Hydrophilized polydiorganosiloxane vinylic crosslinkers and uses thereof

ABSTRACT

The invention provides a hydrophilized polydiorganosiloxane vinylic crosslinker which comprises (1) a polydiorganosiloxane polymer chain comprising dimethylsiloxane units and hydrophilized siloxane units each having one methyl substituent and one monovalent C 4 -C 40  organic radical substituent having two to six hydroxyl groups, wherein the molar ratio of the hydrophilized siloxane units to the dimethylsiloxane units is from about 0.035 to about 0.15, and (2) two terminal (meth)acryloyl groups. The hydrophilized polydiorganosiloxane vinylic crosslinker has a number average molecular weight of from about 3000 Daltons to about 80,000 Daltons. The present invention is also related to a silicone hydrogel contact lens, which comprises repeating units derived from a hydrophilized polydiorganosiloxane vinylic crosslinker of the invention.

This application is a continuation of U.S. patent application Ser. No.16/110,194 filed 23 Aug. 2018, which is a divisional application of U.S.patent application Ser. No. 15/376,700 filed 13 Dec. 2016, now U.S. Pat.No. 10,081,697, which claims the benefit under 35 USC § 119 (e) of U.S.provisional application No. 62/267,310 filed 15 Dec. 2015, hereinincorporated by reference in its entirety.

The present invention is related to a hydrophilized polydiorganosiloxanevinylic crosslinker, to silicone hydrogel contact lenses comprisingrepeating units of such a hydrophilized polydiorganosiloxane vinyliccrosslinker, as well as a method for producing silicone hydrogel contactlenses from such a hydrophilized polydiorganosiloxane vinyliccrosslinker.

BACKGROUND

In recent years, soft silicone hydrogel contact lenses become more andmore popular because of their high oxygen permeability and comfort.“Soft” contact lenses can conform closely to the shape of the eye, sooxygen cannot easily circumvent the lens. Soft contact lenses must allowoxygen from the surrounding air (i.e., oxygen) to reach the corneabecause the cornea does not receive oxygen from the blood supply likeother tissue. If sufficient oxygen does not reach the cornea, cornealswelling occurs. Extended periods of oxygen deprivation cause theundesirable growth of blood vessels in the cornea. By having high oxygenpermeability, a silicone hydrogel contact lens allows sufficient oxygenpermeate through the contact lens to the cornea and to have minimaladverse effects on corneal health.

One of lens forming materials widely used in making silicone hydrogelcontact lenses is a polydiorganosiloxane (e.g., polydimethylsiloxane)vinylic crosslinker which can provide high oxygen permeability toresultant contact lenses. But, a polydimethylsiloxane vinyliccrosslinker can affect the mechanical properties, e.g., elastic modulus,of the resultant contact lenses. For example, a low molecular weightpolydimethylsiloxane vinylic crosslinker (<2,000 g/mol) may provide aresultant contact lens with a relatively high elastic modulus in orderto achieve a desired oxygen permeability. A relative high molecularweight polydimethylsiloxane vinylic crosslinker is typically requiredfor achieving both the high oxygen permeability and the low elasticmodulus. However, because of its hydrophobic nature, apolydimethylsiloxane vinylic crosslinker, especially one with highmolecular weight, is not compatible with hydrophilic components in alens formulation, including, e.g., N,N-dimethylacrylamide,N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or an internal wettingagent. It would be difficult to obtain homogeneous lens formulations(i.e., clear lens formulations) from use of such a polydimethylsiloxanevinylic crosslinker.

It would be even more difficult to obtain a homogeneous, solventlesslens formulation from use of such a polydimethylsiloxane vinyliccrosslinker. Use of organic solvents in preparing silicone hydrogelcontact lens can be costly and is not environmentally friendly.

Therefore, there is a need for new hydophilized polydiorganosiloxanevinylic crosslinkers suitable for preparing a solventless lensformulation that can be used to produce silicone hydrogel contact lenseswith long thermal stability.

Documents, including U.S. Pat. Nos. 4,260,725, 5,034,461, 5,346,946,5,416,132, 5,449,729, 5,486,579, 5,512,205, 5,760,100, 5,994,488,6,858,218, 6,867,245, 7,671,156, 7,744,785, 8,129,442, 8,163,206,8,501,833, 8,513,325, 8,524,850, 8,835,525, 8,993,651, and 9,187,601 andU.S. Pat. Appli. Pub. No. 2016/0090432 A1, disclose that various lensformulations (which are either solvent-containing or solventlessformulations) comprising one or more hydrophilized polysiloxanecrosslinkers can be used for making silicone hydrogel contact lenses.

SUMMARY OF THE INVENTION

The present invention, in one aspect, provides a hydrophilizedpolydiorganosiloxane vinylic crosslinker. The hydrophilizedpolydiorganosiloxane vinylic crosslinker of the invention comprises: (1)a polydiorganosiloxane polymer chain comprising dimethylsiloxane unitsand hydrophilized siloxane units each having one methyl substituent andone monovalent C₄-C₄₀ organic radical substituent having 2 to 6 hydroxylgroups, wherein the molar ratio of the hydrophilized siloxane units tothe dimethylsiloxane units is from about 0.035 to about 0.15; (2) twoterminal (meth)acryloyl groups, wherein the hydrophilizedpolydiorganosiloxane vinylic crosslinker has a number average molecularweight of from about 3000 Daltons to about 80,000 Daltons.

In another aspect, the invention provides a silicone hydrogel contactlens comprising a crosslinked polymeric material comprising: units of ahydrophilized polydiorganosiloxane vinylic crosslinker of the invention(described above), units of a siloxane-containing vinylic monomer, unitsof at least one hydrophilic vinylic monomer, wherein the siliconehydrogel contact lens, when being fully hydrated, has an oxygenpermeability (Dk) of at least about 70 barrers, a water content of fromabout 25% to about 70% by weight, and an elastic modulus of from about0.2 MPa to about 1.2 MPa.

In a further aspect, the present invention provides a method forproducing silicone hydrogel contact lenses. The method comprises thesteps of: preparing a lens-forming composition which is clear at roomtemperature and optionally but preferably at a temperature of from about0 to about 4° C., wherein the lens-forming composition comprises (a)from about 5% to about 35% by weight of a hydrophilizedpolydiorganosiloxane vinylic crosslinker of the invention, (b) asiloxane-containing vinylic monomer, (c) from about 30% to about 60% byweight of at least one hydrophilic vinylic monomer, (d) at least onefree-radical initiator, provided that the above-listed polymerizablecomponents and any additional polymerizable components add up to 100% byweight; introducing the lens-forming composition into a mold, whereinthe mold has a first mold half with a first molding surface defining theanterior surface of a contact lens and a second mold half with a secondmolding surface defining the posterior surface of the contact lens,wherein said first and second mold halves are configured to receive eachother such that a cavity is formed between said first and second moldingsurfaces; curing thermally or actinically the lens-forming compositionin the lens mold to form a silicone hydrogel contact lens, wherein thesilicone hydrogel contact lens has an oxygen permeability (Dk) of atleast about 70 barrers, a water content of from about 25% to about 70%by weight, and an elastic modulus of from about 0.2 MPa to about 1.2MPa.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures are well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references. Wherea term is provided in the singular, the inventors also contemplate theplural of that term. The nomenclature used herein and the laboratoryprocedures described below are those well known and commonly employed inthe art.

“About” as used herein means that a number referred to as “about”comprises the recited number plus or minus 1-10% of that recited number.

“Contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case. A contact lens can be of anyappropriate material known in the art or later developed, and can be asoft lens, a hard lens, or a hybrid lens. A “silicone hydrogel contactlens” refers to a contact lens comprising a silicone hydrogel material.

A “hydrogel” or “hydrogel material” refers to a crosslinked polymericmaterial which is insoluble in water, but can absorb at least 10 percentby weight of water.

A “silicone hydrogel” refers to a silicone-containing hydrogel obtainedby copolymerization of a polymerizable composition comprising at leastone silicone-containing vinylic monomer or at least onesilicone-containing vinylic macromer or at least oneactinically-crosslinkable silicone-containing prepolymer.

“Hydrophilic,” as used herein, describes a material or portion thereofthat will more readily associate with water than with lipids.

A “vinylic monomer” refers to a compound that has one sole ethylenicallyunsaturated group and is soluble in a solvent.

The term “soluble”, in reference to a compound or material in a solvent,means that the compound or material can be dissolved in the solvent togive a solution with a concentration of at least about 0.5% by weight atroom temperature (i.e., a temperature of about 20° C. to about 30° C.).

The term “insoluble”, in reference to a compound or material in asolvent, means that the compound or material can be dissolved in thesolvent to give a solution with a concentration of less than 0.005% byweight at room temperature (as defined above).

The term “olefinically unsaturated group” or “ethylenically unsaturatedgroup” is employed herein in a broad sense and is intended to encompassany groups containing at least one >C═C<group. Exemplary ethylenicallyunsaturated groups include without limitation (meth)acryloyl

allyl, vinyl, styrenyl, or other C═C containing groups.

The term “ene group” refers to a monovalent radical comprising CH₂═CH—that is not covalently attached to an oxygen or nitrogen atom or acarbonyl group.

As used herein, “actinically” in reference to curing, crosslinking orpolymerizing of a polymerizable composition, a prepolymer or a materialmeans that the curing (e.g., crosslinked and/or polymerized) isperformed by actinic irradiation, such as, for example, UV/visibleirradiation, ionizing radiation (e.g. gamma ray or X-ray irradiation),microwave irradiation, and the like. Thermal curing or actinic curingmethods are well-known to a person skilled in the art.

The term “(meth)acrylamide” refers to methacrylamide and/or acrylamide.

The term “(meth)acrylate” refers to methacrylate and/or acrylate.

The term “(meth)acryloxy” refers to a group of

The term “(meth)acrylamido” refers to a group of

in which R′ is hydrogen or C₁-C₁₀-alkyl.

A “hydrophilic vinylic monomer”, as used herein, refers to a vinylicmonomer which as a homopolymer typically yields a polymer that iswater-soluble or can absorb at least 10 percent by weight water.

A “hydrophobic vinylic monomer”, as used herein, refers to a vinylicmonomer which as a homopolymer typically yields a polymer that isinsoluble in water and can absorb less than 10 percent by weight water.

A “blending vinylic monomer” refers to a vinylic monomer capable ofdissolving both hydrophilic and hydrophobic components of apolymerizable composition to form a solution.

A “macromer” or “prepolymer” refers to a compound or polymer thatcontains ethylenically unsaturated groups and has a number averagemolecular weights greater than 700 Daltons.

A “polymer” means a material formed by polymerizing/crosslinking one ormore vinylic monomers, macromers and/or prepolymers.

“Molecular weight” of a polymeric material (including monomeric ormacromeric materials), as used herein, refers to the number-averagemolecular weight unless otherwise specifically noted or unless testingconditions indicate otherwise.

The term “alkyl” refers to a monovalent radical obtained by removing ahydrogen atom from a linear or branched alkane compound. An alkyl group(radical) forms one bond with one other group in an organic compound.

The term “alkylene” refers to a divalent radical obtained by removingone hydrogen atom from an alkyl. An alkylene group (or radical) formstwo bonds with other groups in an organic compound.

In this application, the term “substituted” in reference to an alkylenedivalent radical or an alkyl radical means that the alkylene divalentradical or the alkyl radical comprises at least one substituent whichreplaces one hydrogen atom of the alkylene or alkyl radical and isselected from the group consisting of hydroxyl, carboxyl, —NH₂,sulfhydryl, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio (alkyl sulfide),C₁-C₄ acylamino, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino, halogen atom (Bror Cl), and combinations thereof.

In this application, the term “siloxane unit” refers to a divalentradical of —Si(¹R²R)—O— which has only two substituents, ¹R and ²R whichindependently of each other are monovalent organic radicals and directlylinked via one single bond to the silicon atom of the siloxane unit.

The term “monovalent organic radical” refers to a monovalent radicalobtained by removing a hydrogen atom from an organic compound.

In this application, the term “methyl substituent” in reference to asiloxane unit refers to a methyl radical directly linked to the siliconatom of the siloxane unit; the term “monovalent C₄-C₄₀ organic radicalsubstituent” in reference to a siloxane unit refers to a monovalentorganic radical which comprises 4 to 40 carbon atoms and is directlylinked to the silicon atom of the siloxane unit.

In this application, the term “hydrophilized siloxane unit” refers to asiloxane unit in which one of the two substituents on the silicon atomof the siloxane unit is a monovalent C₄-C₄₀ organic radical having atleast one hydrophilic group or moiety (such as, hydroxyl, methoxy,carboxyl or amino group, or amide or amino bond).

In this application, a “hydrophilized polydiorganosiloxane vinyliccrosslinker” refers to a polydiorganosiloxane vinylic crosslinkercomprising at least one hydrophilized siloxane unit.

As used herein, the term “multiple” refers to three or more.

A “vinylic crosslinker” refers to a compound having at least twoethylenically-unsaturated groups. A “vinylic crossliking agent” refersto a compound with two or more ethylenically unsaturated groups and withmolecular weight less than 700 Daltons.

A free radical initiator can be either a photoinitiator or a thermalinitiator. A “photoinitiator” refers to a chemical that initiates freeradical crosslinking/polymerizing reaction by the use of light. A“thermal initiator” refers to a chemical that initiates radicalcrosslinking/polymerizing reaction by the use of heat energy.

A “polymerizable UV-absorbing agent” or “UV-absorbing vinylic monomer”refers to a compound comprising an ethylenically-unsaturated group and aUV-absorbing moiety.

A “UV-absorbing moiety” refers to an organic functional group which canabsorb or screen out UV radiation in the range from 200 nm to 400 nm asunderstood by a person skilled in the art.

A “spatial limitation of actinic radiation” refers to an act or processin which energy radiation in the form of rays is directed by, forexample, a mask or screen or combinations thereof, to impinge, in aspatially restricted manner, onto an area having a well definedperipheral boundary. A spatial limitation of UV/visible radiation isobtained by using a mask or screen having a radiation (e.g., UV/visible)permeable region, a radiation (e.g., UV/visible) impermeable regionsurrounding the radiation-permeable region, and a projection contourwhich is the boundary between the radiation-impermeable andradiation-permeable regions, as schematically illustrated in thedrawings of U.S. Pat. No. 6,800,225 (FIGS. 1-11), and U.S. Pat. No.6,627,124 (FIGS. 1-9), U.S. Pat. No. 7,384,590 (FIGS. 1-6), and U.S.Pat. No. 7,387,759 (FIGS. 1-6), all of which are incorporated byreference in their entireties. The mask or screen allows to spatiallyprojects a beam of radiation (e.g., UV/visible radiation) having across-sectional profile defined by the projection contour of the mask orscreen. The projected beam of radiation (e.g., UV/visible radiation)limits radiation (e.g., UV/visible radiation) impinging on alens-forming material located in the path of the projected beam from thefirst molding surface to the second molding surface of a mold. Theresultant contact lens comprises an anterior surface defined by thefirst molding surface, an opposite posterior surface defined by thesecond molding surface, and a lens edge defined by the sectional profileof the projected UV/visible beam (i.e., a spatial limitation ofradiation). The radiation used for the crosslinking is any radiationenergy, especially UV/visible radiation, gamma radiation, electronradiation or thermal radiation, the radiation energy preferably being inthe form of a substantially parallel beam in order on the one hand toachieve good restriction and on the other hand efficient use of theenergy.

In the conventional cast-molding process, the first and second moldingsurfaces of a mold are pressed against each other to form acircumferential contact line which defines the edge of a result contactlens. Because the close contact of the molding surfaces can damage theoptical quality of the molding surfaces, the mold cannot be reused. Incontrast, in the Lightstream Technology™, the edge of a resultantcontact lens is not defined by the contact of the molding surfaces of amold, but instead by a spatial limitation of radiation. Without anycontact between the molding surfaces of a mold, the mold can be usedrepeatedly to produce high quality contact lenses with highreproducibility.

“Dye” means a substance that is soluble in a lens-forming fluid materialand that is used to impart color. Dyes are typically translucent andabsorb but do not scatter light.

A “pigment” means a powdered substance (particles) that is suspended ina lens-forming composition in which it is insoluble.

“Surface modification” or “surface treatment”, as used herein, meansthat an article has been treated in a surface treatment/modificationprocess prior to or posterior to the formation of the article, in which(1) a coating is applied to the surface of the article, (2) chemicalspecies are adsorbed onto the surface of the article, (3) the chemicalnature (e.g., electrostatic charge) of chemical groups on the surface ofthe article are altered, or (4) the surface properties of the articleare otherwise modified. Exemplary surface treatment processes include,but are not limited to, a surface treatment by energy (e.g., a plasma, astatic electrical charge, irradiation, or other energy source), chemicaltreatments, the grafting of hydrophilic vinylic monomers or macromersonto the surface of an article, mold-transfer coating process disclosedin U.S. Pat. No. 6,719,929 (herein incorporated by reference in itsentirety), the incorporation of wetting agents into a lens formulationfor making contact lenses proposed in U.S. Pat. Nos. 6,367,929 and6,822,016 (herein incorporated by references in their entireties),reinforced mold-transfer coating disclosed in U.S. Pat. No. 7,858,000(herein incorporated by reference in its entirety), and a hydrophiliccoating composed of covalent attachment or physical deposition of one ormore layers of one or more hydrophilic polymer onto the surface of acontact lens disclosed in U.S. Pat. Nos. 8,147,897 and 8,409,599 and USPat. Appl. Pub. Nos. 2011/0134387, 2012/0026457 and 2013/0118127 (hereinincorporated by references in their entireties).

“Post-curing surface treatment”, in reference to a silicone hydrogelmaterial or a soft contact lens, means a surface treatment process thatis performed after the formation (curing) of the hydrogel material orthe soft contact lens in a mold.

A “hydrophilic surface” in reference to a silicone hydrogel material ora contact lens means that the silicone hydrogel material or the contactlens has a surface hydrophilicity characterized by having an averagedwater contact angle of about 90 degrees or less, preferably about 80degrees or less, more preferably about 70 degrees or less, morepreferably about 60 degrees or less.

An “average contact angle” refers to a water contact angle (measured bySessile Drop), which is obtained by averaging measurements of at least 3individual contact lenses.

The intrinsic “oxygen permeability”, Dk, of a material is the rate atwhich oxygen will pass through a material. As used in this application,the term “oxygen permeability (Dk)” in reference to a hydrogel (siliconeor non-silicone) or a contact lens means a measured oxygen permeability(Dk) which is corrected for the surface resistance to oxygen flux causedby the boundary layer effect according to the procedures shown inExamples hereinafter. Oxygen permeability is conventionally expressed inunits of barrers, where “barrer” is defined as [(cm³oxygen)(mm)/(cm²)(sec)(mm Hg)]×10⁻¹⁰.

The “oxygen transmissibility”, Dk/t, of a lens or material is the rateat which oxygen will pass through a specific lens or material with anaverage thickness of t [in units of mm] over the area being measured.Oxygen transmissibility is conventionally expressed in units ofbarrers/mm, where “barrers/mm” is defined as [(cm³ oxygen)/(cm²)(sec)(mmHg)]×10⁻⁹.

The term “thermal stability” in reference to a silicone hydrogel contactlens means that the silicone hydrogel contact lens can be subjected upto 19 cycles of autoclaves (each for 30 minutes at 121° C.) in aphosphate-buffered saline (7.2±0.2) without significantautoclave-induced change (i.e., an increase or decrease) of about 10% orless, preferably about 5% or less) in at least one lens propertyselected from the group consisting of: elastic modulus E′ (MPa), watercontent (WC %), lens diameter D_(lens) (mm), and combinations thereof,relative to the corresponding lens property of the silicone hydrogelcontact lens which is subjected to one sole autoclave for 30 minutes at121° C.) in a phosphate-buffered saline (7.2±0.2). For example, theautoclave-induced change in a lens property (ΔLP_(AC) ) is calculatedbased on the following equation

${\Delta\;\overset{\_}{{LP}_{AC}}} = {\frac{\overset{\_}{{LP}_{n{AC}}} - \overset{\_}{{LP}_{1{AC}}}}{\overset{\_}{{LP}_{1{AC}}}}}$in which LP_(1AC) is the averaged value of the after-one-autoclave lensproperty of the soft contact lens and is obtained by averaging thevalues of the lens property of 15 soft contact lenses measured afterbeing autoclaved one sole time for 30 minutes at 121° C. in a phosphatebuffered saline at a pH of 7.2±0.2 and LP_(nAC) is the averaged value ofthe after-n-autoclaves lens property of the soft contact lens and isobtained by averaging the values of the lens property of 15 soft contactlenses measured after being stored and n cycles (times) of autoclaveseach for 30 minutes at 121° C. in a phosphate buffered saline at a pH of7.2±0.2. It is believed that the tests of autoclave-induced change inelastic modulus of silicone hydrogel contact lenses can be used inreplacing traditional accelerated shelf-life studies at elevatedtemperature (e.g., 65° C. to 95° C.), in order to shorten significantlythe time required for determining the equivalent shelf-life at roomtemperature.

As used in this application, the term “clear” in reference to alens-forming composition means that the lens-forming composition is atransparent solution or liquid mixture (i.e., having a lighttransmissibility of 85% or greater, preferably 90% or greater in therange between 400 to 700 nm).

In general, the invention is directed to a class of hydrophilizedpolydiorganosiloxane vinylic crosslinkers which each comprise (1) apolydiorganosiloxane polymer chain comprising dimethylsiloxane units andhydrophilized siloxane units each having one methyl substituent and onemonovalent C₄-C₄₀ organic radical substituent having two to six hydroxylgroups, wherein the molar ratio of the hydrophilized siloxane units tothe dimethylsiloxane units is from about 0.035 to about 0.15; (2) twoterminal (meth)acryloyl groups, wherein the hydrophilizedpolydiorganosiloxane vinylic crosslinker has a number average molecularweight of from about 3000 Daltons to about 80,000 Daltons.

This invention is partly based on the discovery that a hydrophilizedpolydiorganosiloxane vinylic crosslinker of the invention is suitablefor preparing various solvent-containing or solventless lensformulations which can contain a large amount of hydrophilicpolymerizable component and are still clear at room temperature or evenat a low storage temperature of from about 0° C. to about 4° C. It isbelieved that a hydrophilized polydiorganosiloxane vinylic crosslinkerof the invention can contain a relatively-large amount of hydroxyl groupper molecule and thereby should be more compatible with otherhydrophilic polymerizable components (e.g., hydrophilic vinylic monomer,hydrophilic crosslinking agent, and/or hydrophilic prepolymer), becauseof the hydrogen-bonding capability of hydroxyl group. With itscapability of being stored at a low storage temperature of from about 0°C. to about 4° C., such a lens formulation can be advantageouslyprepared in advance in the production.

This invention is also partly based on the discovery that apolydiorganosiloxane vinylic crosslinker of the invention (i.e., havingan unique combination of a selected molar ratio of hydrophilizedsiloxane units over dimethylsiloxane units and a selected number averagemolecular weight) can be used in a lens formulation containing arelatively large amount of hydrophilic polymerizable components toproduce silicone hydrogel contact lens which can have a relatively-highoxygen permeability and a relatively low-elastive modulus. It isbelieved that in order to achieve a higher oxygen permeabily, apolydiorganosiloxane should have at least 5 dimethylsiloxane units in aconsecutive sequence. By packing densely hydroxyl groups into a limitednumber of siloxane units, a hydrophilized polydiorganosiloxane vinyliccrosslinker of the invention can have a relatively low molar ratio ofhydrophilized siloxane units over dimethylsiloxane units, ensuring thatsiloxane segments consists of more than 5 consecuive dimethylsiloxaneunits. By selecting a combination of a molar ratio of hydrophilizedsiloxane units over dimethylsiloxane units and a molecular weight, apolydiorganosiloxane vinylic crosslinker of the invention can have arelatively-high contribution to oxygen permeability per siloxane unit, arelatively-high compatibility with hydrophilic polymerizable componentsdue to a large number of hydroxyl groups per molecule, and arelatively-low elastic modulus contribution due to the relatively largemolecular weight.

When a hydrophilized polydiorganosiloxane vinylic crosslinker of theinvention is used in a silicone hydrogel lens formulation, siliconehydrogel contact lenses obtained from the lens formulation can havesuperior lens stability, because of stable backbones of thepolydiorganosiloxane polymer chains and the monovalent C₄-C₄₀ organicradical substituent of hydrophilized siloxane units. A hydrophilizedpolydiorganosiloxane vinylic crosslinker of the invention is designed tohave stable backbones and side chains, free of unstable bonds (such as,urea bond, urethane bond, polyethylene glycol segment) which aresusceptible of cleavage due to hydrolysis, photolysis, poor thermalstability, and/or oxidation.

The present invention, in one aspect, provides a polydiorganosiloxanevinylic crosslinker. The polydiorganosiloxane vinylic crosslinker of theinvention comprises: (1) a polydiorganosiloxane polymer chain comprisingdimethylsiloxane units and hydrophilized siloxane units each having onemethyl substituent and one monovalent C₄-C₄₀ organic radical substituenthaving two to six hydroxyl groups, wherein the molar ratio of thehydrophilized siloxane units to the dimethylsiloxane units is from about0.035 to about 0.15; (2) two terminal (meth)acryloyl groups, wherein thepolydiorganosiloxane vinylic crosslinker has a number average molecularweight of from about 3000 Daltons to about 80,000 Daltons (preferablyfrom about 4000 Daltons to about 50,000 Dalton, more preferably fromabout 5000 Daltons to about 25,000 Daltons, even more preferably fromabout 6000 Daltons to about 18,000 Daltons).

In accordance with a preferred embodiment, a polydiorganosiloxanevinylic crosslinker of the invention is a polymer of formula (1)

in which:

-   -   ν1 is an integer of from 30 to 500 and ω1 is an integer of from        1 to 75, provided that    -   ω1/ν1 is from about 0.035 to about 0.15 (preferably from about        0.040 to about 0.12,    -   even more preferably from about 0.045 to about 0.10);    -   X₀ is O or NR′ in which R′ is hydrogen or C₁-C₁₀-alkyl;    -   R₁ is hydrogen or methyl;    -   R₂ and R₃ independently of each other are a substituted or        unsubstituted C₁-C₁₀ alkylene divalent radical or a divalent        radical of —R₅—O—R₆— in which R₅ and R₆ independently of each        other are a substituted or unsubstituted C₁-C₁₀ alkylene        divalent radical;    -   R₄ is a monovalent radical of any one of formula (2) to (6)

-   -   q1 is zero or 1;    -   n1 is an integer of 2 to 4;    -   n2 is an integer of 1 to 5;    -   n3 is an integer of 3 to 6;    -   n4 is an integer of 2 to 5    -   R₇ is hydrogen or methyl;    -   R₈ and R₉ independent of each other are a C₂-C₆ hydrocarbon        radical having (n2+1) valencies;    -   R₁₀ is ethyl or hydroxymethyl;    -   R₁₁ is methyl or hydromethyl;    -   R₁₂ is hydroxyl or methoxy;    -   X₁ is a sulfur linkage of —S— or a teriary amino linkage of        —NR₁₃— in which R₁₃ is C₁-C₁ alkyl, hydroxyethyl, hydroxypropyl,        or 2,3-dihydroxypropyl; and    -   X₂ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.

In a preferred embodiment, R₄ is a monovalent radical of one of formula(2a) to (2y).

in which q1 is zero or 1 (preferably 1), n1 is an integer of 2 to 4(preferably 3), R₇ is hydrogen or methyl (preferably hydrogen).

In another preferred embodiment, R₄ a monovalent radical of one offormula (3a) to (3y).

in which X₂ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.

In another preferred embodiment, R₄ is a monovalent radical of formula(4a) or (4b).

In another preferred embodiment, R₄ a monovalent radical of one offormula (5a) to (5c).

In another preferred embodiment, the monovalent radical R₄ is a radicalof formula (6) in which n1 is 3 and q1 is 1.

A polydiorganosiloxane vinylic crosslinker of formula (1) can beprepared by reacting a hydrosiloxane-containing polydiorganosiloxane offormula (7) with an ene monomer containing 2 to 5 hydroxyl group

in which X₀, R₁, R₂, R₃, ν1, and ω1 are as defined above, in aplatinum-catalyzed hydrosilylation reaction as known to a person skilledin the art.

Hydrosiloxane-containing polysiloxane of formula (7) can be preparedaccording to any methods known to a person skilled in the art. As anillustrative example, a hydrosiloxane-containing polysiloxane of formula(7) can be prepared from polymerization of a mixture ofoctamethylcyclotetrasiloxane (D4) and1,3,5,7-tetramethylcyclotetrasiloxane (H4) in presence of1,3-bis[3-(meth)acryloxypropyl] tetramethyldisiloxane as a chain endblock and in the presence of a catalyst. By controlling the molar ratioof D4 to H4, a desired value of υ1/ω1 can be obtained.

Where in formula (1) R₄ is a monovalent radical of formula (4), (5) or(6), the ene monomer preferred is 3-allyoxy-1,2-propanediol,2-allyloxymethyl-2-(hydroxymethyl)-1,3-propanediol,2-allyloxymethyl-2-ethyl-1,3-propanediol (i.e.,trimethylolpropaneallylether), allyl α-D-mannopyranoside, allylα-D-galactopyranoside, allyl 6-deoxyhexopyranoside, allyl6-deoxy-2-O-methylhexopyranoside, or a fully-hydrolized (i.e.,ring-opening) product of an epoxy-containing ene monomer which isallyloxy glycidyl ether, 1,2-ppoxy-5-hexene, 3,4-epoxy-1-butene, or2-methyl-2-vinyloxirane. The above-listed ene monomers are commerciallyavailable.

Where in formula (1) R₄ is a monovalent radical of formula (2), the enemonomer preferred is a reaction product of an epoxy-containing enemonomer with a mercaptan having 2 to 5 hydroxyl groups or a secondaryamine having 2 to 5 hydroxyl groups. Examples of commercially availableepoxy-containing ene monomers include without limitation allyloxyglycidyl ether, 1,2-ppoxy-5-hexene, 3,4-epoxy-1-butene, and2-methyl-2-vinyloxirane. Examples of commercially available mercaptanshaving 2 to 4 hydroxyl groups include without limitation1-mercaptoethane-1,2-diol, 2-mercaptopropane-1,3-diol,3-mercaptopropane-1,2-diol, 3-mercaptobutane-1,2-diol,1-mercaptobutane-2,3-diol, 4-mercapto-1,2,3-butanetriol, and2-mercapto-6-methylol-tetrahydropyran-3,4,5-triol. Examples ofcommercially available secondary amines having 2 to 4 hydroxyl groupsinclude without limitation bis(2-hydroxyethyl)amine,bis(2-hydroxypropyl)amine, bis(3-hydroxypropyl)amine,bis-(2,3-dihydroxypropyl)amine, isopropylamino-1,2-propanediol,2-(2-hydroxethylamino)-2-(hydroxymethyl)-1,3-propanediol,2-(ethylamino)-1,3-butanediol, 6-ethylamino-1,2,4-cyclohexanetriol,3-(methylamino)-6-methylol-tetrahydropyrantriol,3-(ethylamino)-6-methylol-tetrahydropyrantriol,3-methylamino-1,2-propanediol, 2-methylamino-1,3-propanediol,1-(Methylamino)-1,2,3-propanetriol, 4-methylamino-1,2-butanediol,2-methylamino-1,4-butanediol, 2-methylamino-1,3-butanediol,N-methyl-2,3,4-trihydroxybutylamine,N-methyl-2,3,4,5-tetradroxypentylamine,N-methyl-2,3,4,5,6-pentadroxyhexylamine. Reactions between an epoxideand a mercaptan (to form a thiol ether linkage) and between an epoxideand a secondary amine (to form an amino linkage) are well known to aperson skilled in the art and have been described in the literature.

Where in formula (1) R₄ is a monovalent radical of formula (3), the enemonomer preferred is a reaction product of either (1) acarboxy-containing ene monomer with a primary or secondary amine having2 to 5 hydroxyl groups or (2) a primary amino-containing or secondaryamino-containing ene monomer with an alkanoic acid having 2 to 5hydroxyl groups, according to the well-known coupling reaction betweenone carboxylic acid group and one amino (primary or secondary) group inthe presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) andN-hydroxysuccinimide (HO—NHS), to obtain an ene monomer having 2 to 5hydroxyl groups and an amide linkage. Examples of commercially availablecarboxy-containing ene monomers include without limitation 3-butenoicacid, 4-pentenoic acid, 5-hexenoic acid, and 6-heptenoic acid. Examplesof commercially available primary or secondary amino-containing enemonomers include without limitation allylamine, 3-butenylamine,4-pentenylamine, 1-methyl-4-pentenylamine, 5-hexenylamine,5-heptenylamine, 6-heptenylamine, N-ethyl-2-methylallylamine,N-ethylallylamine, N-allylmethylamine, N-allyl-1-pentanamine,N-allyl-2-methyl-1-pentanamine, N-Allyl-2,3-dimethyl-1-pentanamine,N-allyl-1-hexanamine, N-allyl-2-methyl-1-hexanamine, andN-allyl-1-heptanamine. Examples of commercially available alkanoic acidshaving 2 to 5 hydroxyl groups include without limitation2,3-dihydroxy-propanoic acid, 2,3-dihydroxybutanoic acid,3,4-dihydroxybutanoic acid, 2,3,4-trihydroxybutanoic acid,2,4,5-trihydroxypentanoic acid,2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid,3,4,5-trihydroxy-2-methoxypentanoic acid, xylonic acid(2,3,4,5-tetrahydroxypantanoic acid), 3,4,5-trihydroxyhexanoic acid,3,5,6-trihydroxyhexanoic acid, 4,5,6-trihydroxyhexanoic acid,2,4,5,6-tetrahydroxyhexanoic acid, 2,3,4,5-tetrahydroxyhexanoic acid,2,3,4,5,6-pentahydroxyhexanoic acid. Examples of commercially availableprimary amines having 2 to 5 hydroxyl groups include without limitationdihydroxyethylamine, 2,3-dihydropropylamine, 2-amino-1,3-propanediol,2-amino-1,4-butanediol, 2-amino-1,3-butanediol, 4-amino-1,2-butanediol,2-amino-1,3,4-butanetriol, 4-amino-1,2,3-butanetriol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-1,5-pentanediol, and3-amino-6-hydroxymethyl-tetrahydropyran-2,4,5-triol. The above-listedcommercially-available secondary amines having 2 to 5 hydroxyl groupscan be used in the reaction with a carboxy-containing ene monomer toobtain an ene monomer having multiple hydroxyl groups and and an amidelinkage. The reaction between a carboxylic acid group and a primary orsecondary amino group to form an amide linkage is well known to a personskilled in the art and has been described extensively in the literature.

A polydiorganosiloxane vinylic crosslinker of the invention (formula (1)as defined above) can find particular use in preparing a polymer,preferably a silicone hydrogel polymeric material, which is anotheraspect of the invention. A person skilled in the art knows how toprepare a polymer or a silicone hydrogel polymeric material from apolymerizable composition according to any known polymerizationmechanism.

In another aspect, the invention provides a silicone hydrogel contactlens comprising a crosslinked polymeric material comprising: units of apolydiorganosiloxane vinylic crosslinker of formula (1) (as definedabove), units of a siloxane-containing vinylic monomer, units of atleast one hydrophilic vinylic monomer, wherein the silicone hydrogelcontact lens, when being fully hydrated, has an oxygen permeability (Dk)of at least about 70 barrers (preferably at least about 80 barrers, morepreferably at least about 90 barrers, even more preferably at leastabout 100 barrers), a water content of from about 25% to about 70% byweight (preferably from about 30% to about 65% by weight, morepreferably from about 35% to about 60% by weight, even more preferablyfrom about 40% to about 55% by weight), and an elastic modulus of fromabout 0.20 MPa to about 1.2 MPa (preferably from about 0.25 MPa to about1.0 MPa, more preferably from about 0.3 MPa to about 0.9 MPa, even morepreferably from about 0.4 MPa to about 0.8 MPa). Preferably, thesilicone hydrogel contact lens has a thermal stability as characterizedby having an autoclave-induced change

$\frac{\overset{\_}{{LP}_{19{AC}}} - \overset{\_}{{LP}_{1{AC}}}}{\overset{\_}{{LP}_{1{AC}}}}$of about 10% or less (preferably about 8% or less, more preferably about6% or less, even more preferably about 4% or less) in at least one lensproperty (LP) selected from the group consisting of elastic modulus,water content, lens diameter, and combinations thereof, wherein LP_(1AC)is the averaged value of the lens property after one-autoclave and isobtained by averaging the values of the lens property of 15 soft contactlenses measured after being autoclaved one sole time for 30 minutes at121° C. in a phosphate buffered saline at a pH of 7.2±0.2 and LP_(19AC)is the averaged values of the lens property after 19-autoclaves and isobtained by averaging the values of the les properies of 15 soft contactlenses measured after being stored and autoclaved 19 times each for 30minutes at 121° C. in a phosphate buffered saline at a pH of 7.2±0.2.

A person skilled in the art knows well how to measure the oxygenpermeability, oxygen transmissibility, water content, elastic modulus,and lens diameter of silicone hydrogel contact lenses. These lensproperties have been reported by all manufacturers for their siliconehydrogel contact lens products.

Various embodiments of a polydiorganosiloxane vinylic crosslinker offormula (1) (as defined above) should be incorporated into this aspectof the invention.

Any suitable siloxane-containing vinylic monomers can be used in theinvention. A class of preferred siloxane-containing vinylic monomers isthose containing a tris(trialkylsiloxy)silyl group or abis(trialkylsilyloxy)alkylsilyl group. Examples of such preferredsilicone-containing vinylic monomers include without limitation3-acrylamidopropyl-bis(trimethylsiloxy)methylsilane, 3-N-methylacrylamidopropylbis(trimethylsiloxy)methylsilane,N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide,N-[tris(dimethylpropylsiloxy)-silylpropyl]-(meth)acrylamide,N-[tris(dimethylphenylsiloxy)silylpropyl] (meth)acrylamide,N-[tris(dimethylethylsiloxy)silylpropyl] (meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methylacrylamide;N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)acrylamide;N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide;N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide;N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide;N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide;N-[2-hydroxy-3-(3-(t-butyldimethylsilyl) propyloxy)propyl]-2-methylacrylamide;N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;3-methacryloxy propylpentamethyldisiloxane,tris(trimethylsilyloxy)silylpropyl methacrylate (TRIS),(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane),(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane,3-methacryloxyethoxypropyloxy-propyl-bis(trimethylsiloxy)methylsilane,N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate,3-(trimethylsilyl)propylvinyl carbonate,3-(vinyloxycarbonylthio)propyl-tris(trimethyl-siloxy)silane,3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate,3-[tris(trimethylsiloxy)silyl] propyl allyl carbamate,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate,t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinylcarbonate, trimethylsilylmethyl vinyl carbonate, and hydrophlizedsiloxane-containing vinylic monomers disclosed in U.S. Pat. Nos.9,103,965, 9,475,827, and 9,097,840 (herein incorporated by referencesin their entireties) which comprise at least one hydrophilic linkageand/or at least one hydrophilic chain.

Another class of preferred siloxane-containing vinylic monomers ispolycarbosiloxane vinylic monomers (or carbosiloxane vinylic mnomers).Examples of such polycarbosiloxane vinylic monomers or macromers arethose described in U.S. Pat. Nos. 7,915,323 and 8,420,711, in US Pat.Appl. Pub. Nos. 2012/244088, 2012/245249, 2015/0309211, and 2015/0309210(herein incorporated by references in their entireties).

A further class of preferred siloxane-containing vinylic monomers ispolydimethylsiloxane-containing vinylic monomers. Examples of suchpolydimethylsiloxane-containing vinylic monomers aremono-(meth)acryloxy-terminated polydimethylsiloxanes of variousmolecular weight (e.g., mono-3-methacryloxypropyl terminated, mono-butylterminated polydimethylsiloxane ormono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butylterminated polydimethylsiloxane), mono-(meth)acrylamido-terminatedpolydimethylsiloxanes of various molecular weight, or combinationsthereof.

In accordance with the invention, a siloxane-containing vinylic monomeris preferably3-(meth)acryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane,3-(meth)acryloxyethoxypropyloxypropylbis(trimethylsiloxy)methylsilane,3-(meth)acrylamidopropyl-bis(trimethylsiloxy)methylsilane, 3-N-methyl(meth)acrylamidopropylbis(trimethylsiloxy) methylsilane,mono-(meth)acryloxy-terminated polydimethylsiloxanes of variousmolecular weight, mono-(meth)acrylamido-terminated polydimethylsiloxanesof various molecular weight, or a combination thereof.

It is understood that the crosslinked polymeric material of a siliconehydrogel contact lens of the invention can optionally comprise apolydimethylsiloxane vinylic crosslinker so long it is compatible withthe hydrophilic polymerizable components in a lens-forming compositionfor making the silicone hydrogel contact lens.

Examples of preferred hydrophilic vinylic monomers include withoutlimitation N-vinylpyrrolidone, N,N-dimethyl (meth)acrylamide,(meth)acrylamide, hydroxylethyl (meth)acrylamide, N-hydroxypropyl(meth)acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate(GMA), polyethylene glycol (meth)acrylate having a number averagemolecular weight of up to 1500, polyethylene glycol C₁-C₄-alkyl ether(meth)acrylate having a number average molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, N-vinyl formamide, N-vinylacetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide,N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,(meth)acrylic acid, ethylacrylic acid, and combinations thereof.Preferably, the hydrophilic vinylic monomer is a hydrophilic N-vinylmonomer, such as, N-vinylpyrrolidone, N-vinyl-N-methyl acetamide,N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, orcombinations thereof. Even more preferably, the hydrophilic vinylicmonomer is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, orcombinations thereof.

In accordance with the invention, the crosslinked polymeric material ofa silicone hydrogel contact lens of the invention can further compriseunits of a hydrophobic vinylic monomer free of silicone, units of anon-silicone vinylic crosslinker, units of a UV-absorbing vinylicmonomer, or a combination thereof.

Examples of preferred hydrophobic vinylic monomers includemethylacrylate, ethyl-acrylate, propylacrylate, isopropylacrylate,cyclohexylacrylate, 2-ethylhexylacrylate, methylmethacrylate,ethylmethacrylate, propylmethacrylate, vinyl acetate, vinyl propionate,vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride,vinylidene chloride, acrylonitrile, 1-butene, butadiene,methacrylonitrile, vinyl toluene, vinyl ethyl ether,perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornylmethacrylate, trifluoroethyl methacrylate, hexafluoro-isopropylmethacrylate, hexafluorobutyl methacrylate.

Examples of preferred non-silicone crosslinkers include withoutlimitation ethyleneglycol di-(meth)acrylate, diethyleneglycoldi-(meth)acrylate, triethyleneglycol di-(meth)acrylate,tetraethyleneglycol di-(meth)acrylate, glycerol di-(meth)acrylate,1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate,1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolatedi-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)]di-(meth)acrylate, bis[2-(meth)acryloxyethyl] phosphate,trimethylolpropane di-(meth)acrylate, and3,4-bis[(meth)acryloyl]tetrahydrofuan, diacrylamide (i.e.,N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e.,N-(1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide),N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine,N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide,N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-propylenebis(meth)acrylamide, N,N′-2-hydroxypropylene bis(meth)acrylamide,N,N′-2,3-dihydroxybutylene bis(meth)acrylamide,1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate (i.e.,N,N′-2-phosphonyloxypropylene bis(meth)acrylamide), piperazinediacrylamide (or 1,4-bis(meth)acryloyl piperazine), vinyl methacrylate,allylmethacrylate, allylacrylate, N-allyl-methacrylamide,N-allyl-acrylamide, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, triallyl isocyanurate, triallyl cyanurate, trimethylopropanetrimethacrylate, pentaerythritol tetramethacrylate, bisphenol Adimethacrylate, a product of diamine (preferably selected from the groupconsisting of N,N′-bis(hydroxyethyl)ethylenediamine,N,N′-dimethylethylenediamine, ethylenediamine,N,N′-dimethyl-1,3-propanediamine, N,N′-diethyl-1,3-propanediamine,propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine,hexamethylenediamine, isophorone diamine, and combinations thereof) andepoxy-containing vinylic monomer (preferably selected from the groupconsisting of glycidyl (meth)acrylate, vinyl glycidyl ether, allylglycidyl ether, and combinations thereof), combinations thereof).

A more preferred crosslinker is selected from the group consisting oftetra(ethyleneglycol) di-(meth)acrylate, tri(ethyleneglycol)di-(meth)acrylate, ethyleneglycol di-(meth)acrylate, di(ethyleneglycol)di-(meth)acrylate, glycerol dimethacrylate, allyl (meth)acrylate,N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide,N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-2-hydroxypropylenebis(meth)acrylamide, N,N′-2,3-dihydroxybutylene bis(meth)acrylamide,1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate (i.e.,N,N′-2-phosphonyloxypropylene bis(meth)acrylamide), piperazinediacrylamide (or 1,4-bis(meth)acryloyl piperazine), triallylisocyanurate, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, and combinations thereof.

Examples of preferred UV-absorbing vinylic monomers include withoutlimitation: 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole,2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl) benzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl-3′-t-butyl-phenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacryloxypropylphenyl) benzotriazole,2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-1),2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-5),3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-2),3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-3),3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate (WL-4),2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-6),2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate (WL-7),4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol(WL-8),2-{2′-Hydroxy-3′-tert-5-[3″-(4″-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole,phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-(UVAM),2-(2′-hydroxy-5′-methacryloxyethyl phenyl) benzotriazole (2-Propenoicacid, 2-methyl-, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethylester, Norbloc),2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole(UV13),2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole(CF₃-UV13), 2-(2′-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole(UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9),2-(2-Hydroxy-3-methallyl-5-methylphenyl)-2H-benzotriazole (UV12),2-3′-t-butyl-2′-hydroxy-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxy-phenyl)-5-methoxybenzotriazole(UV15),2-(2′-hydroxy-5′-methacryloylpropyl-3′-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole(UV16),2-(2′-hydroxy-5′-acryloylpropyl-3′-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole(UV16A), 2-Methylacrylic acid3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propylester (16-100, CAS #96478-15-8),2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethylmethacrylate (16-102); Phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl) (CAS#1260141-20-5);2-[2-Hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole;Phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (9Cl)(CAS #83063-87-0).

In a preferred embodiment, a silicone hydrogel contact lens comprisesfrom about 30% to about 60% by weight of the units of said at least onehydrophilic vinylic monomer, wherein the weight percentage of the unitsof said at least one hydrophilic vinylic monomer is the weightpercentage of said at least one hydrophilic vinylic monomer relative tothe total weight of all polymerizable components in a polymerizablecomposition for making the crosslinked polymeric material.

A silicone hydrogel contact lens can be prepared from a lens-formingcomposition according to a method of the invention which is anotheraspect of the invention.

In a further aspect, the present invention provides a method forproducing silicone hydrogel contact lenses. The method comprises thesteps of: preparing a lens-forming composition which is clear at roomtemperature and optionally but preferably at a temperature of from about0 to about 4° C., wherein the lens-forming composition comprises (a)from about 5% to about 35% by weight of a polydiorganosiloxane vinyliccrosslinker of formula (1) (as defined above), (b) a siloxane-containingvinylic monomer, (c) from about 30% to about 60% by weight of at leastone hydrophilic vinylic monomer, (d) at least one free-radicalinitiator, provided that the above-listed polymerizable components andany additional polymerizable components add up to 100% by weight;introducing the lens-forming composition into a mold, wherein the moldhas a first mold half with a first molding surface defining the anteriorsurface of a contact lens and a second mold half with a second moldingsurface defining the posterior surface of the contact lens, wherein saidfirst and second mold halves are configured to receive each other suchthat a cavity is formed between said first and second molding surfaces;curing thermally or actinically the lens-forming composition in the lensmold to form a silicone hydrogel contact lens, wherein the siliconehydrogel contact lens has an oxygen permeability (Dk) of at least about70 barrers, a water content of from about 25% to about 70% by weight, anelastic modulus of from about 0.2 MPa to about 1.2 MPa, and a thermalstability as characterized by having an autoclave-induced change

$\frac{\overset{\_}{{LP}_{19{AC}}} - \overset{\_}{{LP}_{1{AC}}}}{\overset{\_}{{LP}_{1{AC}}}}$of about 10% or less in at least one lens property (LP) selected fromthe group consisting of elastic modulus, water content, lens diameter,and combinations thereof, wherein LP_(1AC) is the averaged value of thelens property after one-autoclave and is obtained by averaging thevalues of the lens property of 15 soft contact lenses measured afterbeing autoclaved one sole time for 30 minutes at 121° C. in a phosphatebuffered saline at a pH of 7.2±0.2 and LP_(19AC) is the averaged valuesof the lens property after 19-autoclaves and is obtained by averagingthe values of the les properies of 15 soft contact lenses measured afterbeing stored and autoclaved 19 times each for 30 minutes at 121° C. in aphosphate buffered saline at a pH of 7.2±0.2.

Various embodiments described above of a polydiorganosiloxane vinyliccrosslinker of formula (1) (as defined above) should be incorporatedinto this aspect of the invention.

Various embodiments described above of a siloxane-containing vinylicmonomer, a hydrophilic vinylic monomer should be incorporated in thisaspect of the invention.

In accordance with the invention, a free-radical initiator can be athermal initiator or hotoinitiator.

Suitable thermal polymerization initiators are known to the skilledartisan and comprise, for example peroxides, hydroperoxides,azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates ormixtures thereof. Examples are benzoylperoxide, tert.-butyl peroxide,di-tert.-butyl-diperoxyphthalate, tert.-butyl hydroperoxide,azo-bis(isobutyronitrile) (AIBN), 1,1-azodiisobutyramidine, 1,1′-azo-bis(1-cyclohexanecarbonitrile), 2,2′-azo-bis(2,4-dimethyl-valeronitrile)and the like. The polymerization is carried out conveniently in anabove-mentioned solvent at elevated temperature, for example at atemperature of from 25 to 100° C. and preferably 40 to 80° C. Thereaction time may vary within wide limits, but is conveniently, forexample, from 1 to 24 hours or preferably from 2 to 12 hours. It isadvantageous to previously degas the components and solvents used in thepolymerization reaction and to carry out said copolymerization reactionunder an inert atmosphere, for example under a nitrogen or argonatmosphere.

Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone,a benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocurand Irgacur types, preferably Darocur 1173® and Darocur 2959®,Germane-based Norrish Type I photoinitiators. Examples ofbenzoylphosphine initiators include2,4,6-trimethylbenzoyldiphenylophosphine oxide;bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; andbis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactivephotoinitiators which can be incorporated, for example, into a macromeror can be used as a special monomer are also suitable. Examples ofreactive photoinitiators are those disclosed in EP 632 329, hereinincorporated by reference in its entirety. The polymerization can thenbe triggered off by actinic radiation, for example light, in particularUV light of a suitable wavelength. The spectral requirements can becontrolled accordingly, if appropriate, by addition of suitablephotosensitizers.

Where a vinylic monomer capable of absorbing ultra-violet radiation andhigh energy violet light (HEVL) is used in the invention, aGermane-based Norrish Type I photoinitiator and a light source includinga light in the region of about 400 to about 550 nm are preferably usedto initiate a free-radical polymerization. Any Germane-based NorrishType I photoinitiators can be used in this invention, so long as theyare capable of initiating a free-radical polymerization underirradiation with a light source including a light in the region of about400 to about 550 nm. Examples of Germane-based Norrish Type Iphotoinitiators are acylgermanium compounds described in U.S. Pat. No.7,605,190 (herein incorporated by reference in its entirety).Preferably, the monomer of lens-forming materials comprises at least oneof the following acylgermanium compounds.

In a preferred embodiment, the lens-forming composition comprises anorganic solvent.

Example of suitable solvents includes without limitation,tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycolmethyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone,methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethyleneglycol methyl ether, ethylene glycol phenyl ether, propylene glycolmethyl ether, propylene glycol methyl ether acetate, dipropylene glycolmethyl ether acetate, propylene glycol n-propyl ether, dipropyleneglycol n-propyl ether, tripropylene glycol n-butyl ether, propyleneglycol n-butyl ether, dipropylene glycol n-butyl ether, tripropyleneglycol n-butyl ether, propylene glycol phenyl ether dipropylene glycoldimetyl ether, polyethylene glycols, polypropylene glycols, ethylacetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate,i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol,menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol,3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol,2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol,tert-amyl, alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol,3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol,3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol,2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol,2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol,4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol,3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol,3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol,4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol,1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol,3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol,2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol,2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol,1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol,1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethyl formamide,dimethyl acetamide, dimethyl propionamide, N-methyl pyrrolidinone, andmixtures thereof.

In another preferred embodiment, a lens-forming composition is asolution of all the desirable components dissolved in 1-propanol,isopropanol, tert-amyl alcohol, 1,2-propylene glycol, apolyethyleneglycol having a molecular weight of about 400 Daltons orless, or a mixture thereof.

In another preferred embodiment, the lens-forming composition is asolventless liquid mixture and comprises a blending vinylic monomerselected from the group consisting of a C₁-C₁₀ alkyl methacrylate,isobornylmethacrylate, isobornylacrylate, cyclopentylmethacrylate,cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate,styrene, 2,4,6-trimethylstyrene (TMS), and t-butyl styrene (TBS), andcombinations thereof. Preferably, the blending vinylic monomer ismethylmethacrylate.

In another preferred embodiment, the total amount of allsilicone-containing polymerizable components present in the lens-formingcomposition is about 65% or less.

In another preferred embodiment, the hydrophilic vinylic monomer is ahydrophilic N-vinyl monomer, preferably is N-vinylpyrrolidone,N-vinyl-N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide,N-vinyl isopropylamide, or combinations thereof, even more preferably isN-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or combinations thereof.

In another preferred embodiment, the lens-forming composition furthercomprises a non-silicone vinylic crosslinker. Various embodimentsdescribed above of a siloxane-containing vinylic monomer, a hydrophilicvinylic monomer should be incorporated in this aspect of the invention.The amount of a non-silicone vinylic crosslinker used is expressed inthe weight content with respect to the total polymerizable componentsand is preferably in the range from about 0.05% to about 2%, and morepreferably in the range from about 0.1% to about 1.5%, even morepreferably in the range from about 0.15% to about 1.0%.

In accordance with the invention, the lens-forming composition canfurther comprise other components, such as, a visibility tinting agent(e.g., dyes, pigments, or mixtures thereof), antimicrobial agents (e.g.,preferably silver nanoparticles), a bioactive agent, leachablelubricants, leachable tear-stabilizing agents, and mixtures thereof, asknown to a person skilled in the art.

Lens molds for making contact lenses are well known to a person skilledin the art and, for example, are employed in cast molding or spincasting. For example, a mold (for cast molding) generally comprises atleast two mold sections (or portions) or mold halves, i.e. first andsecond mold halves. The first mold half defines a first molding (oroptical) surface and the second mold half defines a second molding (oroptical) surface. The first and second mold halves are configured toreceive each other such that a lens forming cavity is formed between thefirst molding surface and the second molding surface. The moldingsurface of a mold half is the cavity-forming surface of the mold and indirect contact with lens-forming material.

Methods of manufacturing mold sections for cast-molding a contact lensare generally well known to those of ordinary skill in the art. Theprocess of the present invention is not limited to any particular methodof forming a mold. In fact, any method of forming a mold can be used inthe present invention. The first and second mold halves can be formedthrough various techniques, such as injection molding or lathing.Examples of suitable processes for forming the mold halves are disclosedin U.S. Pat. Nos. 4,444,711; 4,460,534; 5,843,346; and 5,894,002, whichare also incorporated herein by reference in their entireties.

Virtually all materials known in the art for making molds can be used tomake molds for making contact lenses. For example, polymeric materials,such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade8007-S10 (clear amorphous copolymer of ethylene and norbornene, fromTicona GmbH of Frankfurt, Germany and Summit, N.J.), or the like can beused. Other materials that allow UV light transmission could be used,such as quartz glass and sapphire.

In accordance with the invention, the lens-forming formulation (orcomposition) can be introduced (dispensed) into a cavity formed by amold according to any known methods.

After the lens-forming composition is dispensed into the mold, it ispolymerized to produce a contact lens. Crosslinking may be initiatedthermally or actinically.

Opening of the mold so that the molded article can be removed from themold may take place in a manner known per se.

The molded contact lens can be subject to lens extraction to removeunpolymerized polymerizable components. The extraction solvent can beany solvent known to a person skilled in the art. Examples of suitableextraction solvent are those described above. Preferably, water or anaqueous solution is used as extraction solvent. After extraction, lensescan be hydrated in water or an aqueous solution of a wetting agent(e.g., a hydrophilic polymer).

The molded contact lenses can further subject to further processes, suchas, for example, surface treatment, packaging in lens packages with apackaging solution which can contain about 0.005% to about 5% by weightof a wetting agent (e.g., a hydrophilic polymer described above or thelike known to a person skilled in the art) and/or a viscosity-enhancingagent (e.g., methyl cellulose (MC), ethyl cellulose,hydroxymethylcellulose, hydroxyethyl cellulose (HEC),hydroxypropylcellulose (HPC), hydroxypropylmethyl cellulose (HPMC), or amixture thereof); sterilization such as autoclave at from 118 to 124° C.for at least about 30 minutes; and the like.

In a preferred embodiment, the resultant silicone hydrogel contact lensis extracted with water or an aqueous solution.

In another preferred embodiment, the mold is a reusable mold and thelens-forming composition is cured (i.e., polymerized) actinically undera spatial limitation of actinic radiation to form a silicone hydrogelcontact lens. Examples of preferred reusable molds are those disclosedin U.S. Pat. Nos. 6,627,124, 6,800,225, 7,384,590, and 7,387,759, whichare incorporated by reference in their entireties. Reusable molds can bemade of quartz, glass, sapphire, CaF₂, a cyclic olefin copolymer (suchas for example, Topas® COC grade 8007-S10 (clear amorphous copolymer ofethylene and norbornene) from Ticona GmbH of Frankfurt, Germany andSummit, N.J., Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville,Ky.), polymethylmethacrylate (PMMA), polyoxymethylene from DuPont(Delrin), Ultem® (polyetherimide) from G.E. Plastics, PrimoSpire®, andcombinations thereof.

Although various embodiments of the invention have been described usingspecific terms, devices, and methods, such description is forillustrative purposes only. The words used are words of descriptionrather than of limitation. It is to be understood that changes andvariations may be made by those skilled in the art without departingfrom the spirit or scope of the present invention, which is set forth inthe following claims. In addition, it should be understood that aspectsof the various embodiments may be interchanged either in whole or inpart or can be combined in any manner and/or used together, asillustrated below:

1. A polydiorganosiloxane vinylic crosslinker, comprising: (1) apolydiorganosiloxane polymer chain comprising dimethylsiloxane units andhydrophilized siloxane units each having one methyl substituent and onemonovalent C₄-C₄₀ organic radical substituent having two to six hydroxylgroups, wherein the molar ratio of the hydrophilized siloxane units tothe dimethylsiloxane units is from about 0.035 to about 0.15; (2) twoterminal (meth)acryloyl groups, wherein the polydiorganosiloxane vinyliccrosslinker has a number average molecular weight of from about 3000Daltons to about 80,000 Daltons.

2. The polydiorganosiloxane vinylic crosslinker according to invention1, wherein the polydiorganosiloxane vinylic crosslinker is a polymer offormula (1)

in which:

ν1 is an integer of from 30 to 500 and ω1 is an integer of from 1 to 75,provided that ω1/ν1 is from about 0.035 to about 0.15;

X₀ is O or NR′ in which R′ is hydrogen or C₁-C₁₀-alkyl;

R₁ is hydrogen or methyl;

R₂ and R₃ independently of each other are a substituted or unsubstitutedC₁-C₁₀ alkylene divalent radical or a divalent radical of —R₅—O—R₆— inwhich R₅ and R₆ independently of each other are a substituted orunsubstituted C₁-C₁₀ alkylene divalent radical;

R₄ is a monovalent radical of any one of formula (2) to (6)

q1 is zero or 1;

n1 is an integer of 2 to 4;

n2 is an integer of 1 to 5;

n3 is an integer of 3 to 6;

n4 is an integer of 2 to 5

R₇ is hydrogen or methyl;

R₈ and R₉ independent of each other are a C₂-C₆ hydrocarbon radicalhaving (n2+1) valencies;

R₁₀ is ethyl or hydroxymethyl;

R₁₁ is methyl or hydromethyl;

R₁₂ is hydroxyl or methoxy;

X₁ is a sulfur linkage of —S— or a teriary amino linkage of —NR₁₃— inwhich R₁₃ is C₁-C₃ alkyl, hydroxylethyl, hydroxypropyl, or2,3-dihydroxypropyl; and

X₂ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.

3. The polydiorganosiloxane vinylic crosslinker according to invention2, wherein in formula (1) ω1/ν1 is from about 0.040 to about 0.12.

4. The polydiorganosiloxane vinylic crosslinker according to invention2, wherein in formula (1) ω1/ν1 is from about 0.045 to about 0.10.

5. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 4, wherein R₄ is a monovalent radical of formula (2).

6. The polydiorganosiloxane vinylic crosslinker according to invention5, wherein R₄ is a monovalent radical of any one of formula (2a) to (2y)

in which q1 is zero or 1, n1 is an integer of 2 to 4, R₇ is hydrogen ormethyl.

7. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 4, wherein R₄ is a monovalent radical of formula (3).

8. The polydiorganosiloxane vinylic crosslinker according to invention7, wherein R₄ is a monovalent radical of any one of formula (3a) to (3y)

in which X₂ is an amide linkage of

in which R₁₄ is hydrogen or C₁-C₁₀ alkyl.

9. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 4, wherein R₄ is a monovalent radical of formula (4).

10. The polydiorganosiloxane vinylic crosslinker according to invention9, wherein R₄ is a monovalent radical of formula (4a) or (4b)

11. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 4, wherein R₄ is a monovalent radical of formula (5).

12. The polydiorganosiloxane vinylic crosslinker according to invention11, wherein R₄ is a monovalent radical of any one of formula (5a) to(5c)

13. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 4, wherein R₄ is a monovalent radical of formula (6).

14. The polydiorganosiloxane vinylic crosslinker according to invention13, wherein in formula (6) n1 is 3 and q1 is 1.

15. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 11, wherein in formula (1) X₀ is O.

16. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 2 to 11, wherein in formula (1) X₀ is NR′ in which R′ ishydrogen or C₁-C₁₀-alkyl.

17. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 1 to 16, wherein the polydiorganosiloxane vinylic crosslinkerhas a number average molecular weight of from about 4000 Daltons toabout 50,000 Dalton.

18. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 1 to 16, wherein the polydiorganosiloxane vinylic crosslinkerhas a number average molecular weight of from about 5000 Daltons toabout 25,000 Daltons.

19. The polydiorganosiloxane vinylic crosslinker according to any one ofinventions 1 to 16, wherein the polydiorganosiloxane vinylic crosslinkerhas a number average molecular weight of from about 6000 Daltons toabout 18,000 Daltons.

20. A silicone hydrogel contact lens comprising a crosslinked polymericmaterial which comprises:

units of a polydiorganosiloxane vinylic crosslinker according to any oneof inventions 1 to 19;

units of a siloxane-containing vinylic monomer;

units of at least one hydrophilic vinylic monomer,

wherein the silicone hydrogel contact lens, when being fully hydrated,has an oxygen permeability (Dk) of at least about 70 barrers, a watercontent of from about 25% to about 70% by weight, and an elastic modulusof from about 0.2 MPa to about 1.2 MPa.

21. The silicone hydrogel contact lens of invention 20, wherein thesilicone hydrogel contact lens has a thermal stability as characterizedby having an autoclave-induced change

$\frac{\overset{\_}{{LP}_{19{AC}}} - \overset{\_}{{LP}_{1{AC}}}}{\overset{\_}{{LP}_{1{AC}}}}$of about 10% or less in at least one lens property (LP) selected fromthe group consisting of elastic modulus, water content, lens diameter,and combinations thereof, wherein LP_(1AC) is the averaged value of thelens property after one-autoclave and is obtained by averaging thevalues of the lens property of 15 soft contact lenses measured afterbeing autoclaved one sole time for 30 minutes at 121° C. in a phosphatebuffered saline at a pH of 7.2±0.2 and LP_(18AC) is the averaged valuesof the lens property after 19-autoclaves and is obtained by averagingthe values of the les properies of 15 soft contact lenses measured afterbeing stored and autoclaved 19 times each for 30 minutes at 121° C. in aphosphate buffered saline at a pH of 7.2±0.2.

22. The silicone hydrogel contact lens according to invention 20 or 21,wherein the hydrophilic vinylic monomer is N-vinylpyrrolidone,N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol(meth)acrylate having a number average molecular weight of up to 1500,polyethylene glycol C₁-C₄-alkyl ether (meth)acrylate having a numberaverage molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, N-vinyl formamide, N-vinylacetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide,N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,(meth)acrylic acid, ethylacrylic acid, or combinations thereof.

23. The silicone hydrogel contact lens according to invention 22,wherein the hydrophilic vinylic monomer is N-vinylpyrrolidone,N-vinyl-N-methyl acetamide, or combinations thereof.

24. The silicone hydrogel contact lens according to any one ofinventions 20 to 23, wherein the crosslinked polymeric material furthercomprises units of a hydrophobic vinylic monomer free of silicone, unitsof a non-silicone vinylic crosslinker, units of a UV-absorbing vinylicmonomer, or a combination thereof.

25. The silicone hydrogel contact lens according to any one ofinventions 20 to 24, wherein the silicone hydrogel contact lenscomprises from about 30% to about 60% by weight of the units of said atleast one hydrophilic vinylic monomer, wherein the weight percentage ofthe units of said at least one hydrophilic vinylic monomer is the weightpercentage of said at least one hydrophilic vinylic monomer relative tothe total weight of all polymerizable components in a polymerizablecomposition for making the crosslinked polymeric material.

26. A method for producing silicone hydrogel contact lenses, comprisingthe steps of:

preparing a lens-forming composition which is clear at room temperatureand optionally but preferably at a temperature of from about 0 to about4° C., wherein the lens-forming composition comprises (a) from about 5%to about 35% by weight of a polydiorganosiloxane vinylic crosslinker ofany one of claims 1 to 19, (b) a siloxane-containing vinylic monomer,(c) from about 30% to about 60% by weight of at least one hydrophilicvinylic monomer, (d) at least one free-radical initiator, provided thatthe above-listed polymerizable components and any additionalpolymerizable components add up to 100% by weight;

introducing the lens-forming composition into a mold, wherein the moldhas a first mold half with a first molding surface defining the anteriorsurface of a contact lens and a second mold half with a second moldingsurface defining the posterior surface of the contact lens, wherein saidfirst and second mold halves are configured to receive each other suchthat a cavity is formed between said first and second molding surfaces;and

curing thermally or actinically the lens-forming composition in the lensmold to form a silicone hydrogel contact lens, wherein the siliconehydrogel contact lens has an oxygen permeability (Dk) of at least about70 barrers, a water content of from about 25% to about 70% by weight,and an elastic modulus of from about 0.2 MPa to about 1.2 MPa,

27. The method of invention 26, wherein the silicone hydrogel contactlens has a thermal stability as characterized by having anautoclave-induced change

$\frac{\overset{\_}{{LP}_{19{AC}}} - \overset{\_}{{LP}_{1{AC}}}}{\overset{\_}{{LP}_{1{AC}}}}$of about 10% or less in at least one lens property (LP) selected fromthe group consisting of elastic modulus, water content, lens diameter,and combinations thereof, wherein LP_(1AC) is the averaged value of thelens property after one-autoclave and is obtained by averaging thevalues of the lens property of 15 soft contact lenses measured afterbeing autoclaved one sole time for 30 minutes at 121° C. in a phosphatebuffered saline at a pH of 7.2±0.2 and LP_(19AC) is the averaged valuesof the lens property after 19-autoclaves and is obtained by averagingthe values of the les properies of 15 soft contact lenses measured afterbeing stored and autoclaved 19 times each for 30 minutes at 121° C. in aphosphate buffered saline at a pH of 7.2±0.2.

28. The method according to invention 26 or 27, wherein the lens-formingcomposition is a solventless liquid mixture and comprises a blendingvinylic monomer selected from the group consisting of a C₁-C₁₀ alkylmethacrylate, isobornylmethacrylate, isobornylacrylate,cyclopentylmethacrylate, cyclopentylacrylate, cyclohexylmethacrylate,cyclohexylacrylate, styrene, 2,4,6-trimethylstyrene (TMS), and t-butylstyrene (TBS), and combinations thereof (preferably, the blendingvinylic monomer is methylmethacrylate).

29. The method according to invention 26 or 27, wherein the lens-formingcomposition comprises an organic solvent (preferably selected from thegroup consisting of 1-propanol, isopropanol, tert-amyl alcohol,1,2-propylene glycol, a polyethyleneglycol having a molecular weight ofabout 400 Daltons or less, or a mixture thereof).

30. The method according to any one of inventions 26 to 29, wherein thetotal amount of all silicone-containing polymerizable components presentin the lens-forming composition is about 65% or less.

31. The method according to any one of inventions 26 to 30, wherein thehydrophilic vinylic monomer is a hydrophilic N-vinyl monomer, preferablyis N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl formamide,N-vinyl acetamide, N-vinyl isopropylamide, or combinations thereof, evenmore preferably is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, orcombinations thereof.

32. The method according to any one of inventions 26 to 31, wherein thelens-forming composition further comprises a non-silicone vinyliccrosslinker.

33. The method according to invention 32, wherein the non-siliconevinylic crosslinker is selected from the group consisting ofethyleneglycol di-(meth)acrylate, diethyleneglycol di-(meth)acrylate,triethyleneglycol di-(meth)acrylate, tetraethyleneglycoldi-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanedioldi-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanedioldi-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate,ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate,bis[2-(meth)acryloxyethyl] phosphate, trimethylolpropanedi-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuan,diacrylamide (i.e., N-(1-oxo-2-propenyl)-2-propenamide),dimethacrylamide (i.e.,N-(1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide),N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine,N,N′-methylene bis(meth)acrylamide, N,N′-ethylene bis(meth)acrylamide,N,N′-dihydroxyethylene bis(meth)acrylamide, N,N′-propylenebis(meth)acrylamide, N,N′-2-hydroxypropylene bis(meth)acrylamide,N,N′-2,3-dihydroxybutylene bis(meth)acrylamide,1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate (i.e.,N,N′-2-phosphonyloxypropylene bis(meth)acrylamide), piperazinediacrylamide (or 1,4-bis(meth)acryloyl piperazine), vinyl methacrylate,allylmethacrylate, allylacrylate, N-allyl-methacrylamide,N-allyl-acrylamide, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, triallyl isocyanurate, triallyl cyanurate, trimethylopropanetrimethacrylate, pentaerythritol tetramethacrylate, bisphenol Adimethacrylate, combinations thereof (preferably selected from the groupconsisting of tetra(ethyleneglycol) di-(meth)acrylate,tri(ethyleneglycol) di-(meth)acrylate, ethyleneglycol di-(meth)acrylate,di(ethyleneglycol) di-(meth)acrylate, glycerol dimethacrylate, allyl(meth)acrylate, N,N′-methylene bis(meth)acrylamide, N,N′-ethylenebis(meth)acrylamide, N,N′-dihydroxyethylene bis(meth)acrylamide,N,N′-2-hydroxypropylene bis(meth)acrylamide, N,N′-2,3-dihydroxybutylenebis(meth)acrylamide, 1,3-bis(meth)acrylamidepropane-2-yl dihydrogenphosphate (i.e., N,N′-2-phosphonyloxypropylene bis(meth)acrylamide),piperazine diacrylamide (or 1,4-bis(meth)acryloyl piperazine), triallylisocyanurate, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, and combinations thereof).

34. The method according to any one of inventions 26 to 33, wherein thesiloxane-containing vinylic monomer is3-(meth)acryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane,3-(meth)acryloxyethoxypropyloxypropylbis(trimethylsiloxy)methylsilane,3-(meth)acrylamidopropyl-bis(trimethylsiloxy)methylsilane, 3-N-methyl(meth)acrylamidopropylbis(trimethylsiloxy) methylsilane,mono-(meth)acryloxy-terminated polydimethylsiloxanes of variousmolecular weight, mono-(meth)acrylamido-terminated polydimethylsiloxanesof various molecular weight, or a combination thereof.

35. The method according to any one of inventions 26 to 34, wherein thestep of curing is carried out thermally.

The previous disclosure will enable one having ordinary skill in the artto practice the invention. Various modifications, variations, andcombinations can be made to the various embodiment described herein. Inorder to better enable the reader to understand specific embodiments andthe advantages thereof, reference to the following examples issuggested. It is intended that the specification and examples beconsidered as exemplary.

The following abbreviations are used in the following examples: MCR-M07represents monobutyl-terminated monomethacryloxypropyl-terminatedpolydimethylsiloxane (M.W. 600 to 800 g/mol from Gelest); NVP representsN-vinylpyrrolidone; DMA represents N,N-dimethylacrylamide; VMArepresents N-vinyl-N-methyl acetamide; N—CH₃ BisAm representsN-methyl-N-bis(trimethylsiloxy)methylsilylpropyl acrylamide (or3-N-methyl (meth)acrylamidopropylbis(trimethylsiloxy) methylsilane);SIGMA represents3-(3-methacryloxy-2-hydroxypropyloxypropyl-bis(trimethylsiloxy)methylsilane;MMA represents methyl methacrylate; TEGDMA represent triethyleneglycoldimethacrylate; TEGDVE represents triethyleneglycol divinyl ether; EGMArepresents ethylene glycol methyl ether methacrylate; AMA representsallyl methacrylate; VAZO 64 represents2,2′-dimethyl-2,2′azodipropiononitrile; Nobloc is2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate fromAldrich; RB246 is Reactive Blue 246 from Arran; 1-PrOH represents1-propanol; IPA represents isopropanol; DC 1173 represents Darocur 1173®photoinitiator; MeCN represents acetonitrile;

Example 1

Oxygen Permeability Measurements

Unless specified, the apparent oxygen permeability (Dk_(app)), theapparent oxygen transmissibility (Dk/t), the intrinsic (oredge-corrected) oxygen permeability (Dk_(c)) of a lens and a lensmaterial are determined according to procedures described in Example 1of U.S. patent application publication No. 2012/0026457 A1 (hereinincorporated by reference in its entirety).

Ion Permeability Measurements

The ion permeability of a lens is measured according to proceduresdescribed in U.S. Pat. No. 5,760,100 (herein incorporated by referencein its entirety. The values of ion permeability reported in thefollowing examples are relative ionoflux diffusion coefficients(D/D_(ref)) in reference to a lens material, Alsacon, as referencematerial. Alsacon has an ionoflux diffusion coefficient of 0.314×10⁻³mm²/minute.

Autoclave

The autoclave is done at 121° C. Each cycle of autoclave takes 30minutes. 15 lenses are subject to 1 cycle of autoclave. 15 lenses aresubjected to 7 cycles of autoclave. 15 lenses are subjected to 13 cyclesof autoclave. 15 lenses are subjected to 19 cycles of autoclave. Thoselenses subjected to n-cycles of autoclave treatments are used for lensproperty characterization to assess lens thermal stability.

Lubricity Evaluation

The lubricity of a lens is evaluated by using a finger-felt lubricitytest which characterizes qualitatively the slipperiness of a lenssurface on a friction rating scale of from 0 to 4. The higher thefriction rating is, the lower the slipperiness (or lubricity).

Commercial lenses: DAILIES® TOTAL1®; ACUVUE® OASYS™; ACUVUE® ADVANCEPLUS™; DAILIES® Aqua Comfort Plus®; and AIR OPTIX®, are assigned afriction rating (designated “FR” hereinafter) of 0, 1, 2, 3, and 4respectively. They are used as standard lenses for determining thefriction rating of a lens under test.

The samples are placed in PBS for at least two rinses of 30 minutes eachand then transferred to fresh PBS before the evaluation. Before theevaluation, hands are rinsed with a soap solution, extensively rinsedwith DI water and then dried with KimWipe® towels. The samples arehandled between the fingers and a numerical number is assigned for eachsample relative to the above standard lenses described above. Forexample, if lenses are determined to be only slightly better than AIROPTIX® lenses, then they are assigned a number 3. The value of afriction rating is one obtained by averaging the results of at least twofriction ratings of a contact lens by two or more persons and/or byaveraging the friction ratings of two or more contact lenses (from theidentical batch of lens production) by one person.

Surface Wettability Tests

Water contact angle (WCA) on a contact lens is a general measure of thesurface wettability of a contact lens. In particular, a low watercontact angle corresponds to more wettable surface. Average contactangles (Sessile Drop) of contact lenses are measured using a VCA 2500 XEcontact angle measurement device from AST, Inc., located in Boston,Mass. This equipment is capable of measuring advancing contact angles(θ_(a)) or receding contact angles (θ_(r)) or sessile (static) contactangles. Unless specified, water contact angle is sessile (static)contact angle. The measurements are performed on fully hydrated contactlenses and immediately after blot-drying as follows. A contact lens isremoved from the vial and washed 3 times in ˜200 ml of fresh DI water inorder to remove loosely bound packaging additives from the lens surface.The lens is then placed on top of a lint-free clean cloth (Alpha WipeTX1009), dabbed well to remove surface water, mounted on the contactangle measurement pedestal, blown dry with a blast of dry air andfinally the sessile drop contact angle is automatically measured usingthe software provided by the manufacturer. The DI water used formeasuring the contact angle has a resistivity >18MΩcm and the dropletvolume used is 2 μl. Typically, uncoated silicone hydrogel lenses (afterautoclave) have a sessile drop contact angle around 120 degrees. Thetweezers and the pedestal are washed well with Isopropanol and rinsedwith DI water before coming in contact with the contact lenses.

Water Break-Up Time (WBUT) Tests

The surface hydrophilicity of lenses (after autoclave) is assessed bydetermining the time required for the water film to start breaking onthe lens surface. Briefly, lenses are removed from the vial and placedin PBS (phosphate buffered saline) for at least two rinses of 30 minuteseach and then transferred to fresh PBS in order to remove loosely boundpackaging additives from the lens surface. The lens is removed from thesolution and held against a bright light source. The time that is neededfor the water film to break (de-wet) exposing the underlying lensmaterial is noted visually. Uncoated lenses typically instantly breakupon removal from PBS and are assigned a WBUT of 0 seconds. Lensesexhibiting WBUT 10 seconds are considered to have a hydrophilic surfaceand are expected to exhibit adequate wettability (ability to support thetear film) on-eye.

Digital Rubbing Tests

The lenses are digitally rubbed (wearing disposable powder-free latexgloves) with PBS or RENU® multi-purpose lens care solution (or anothermulti-purpose lens care solution) for 20 seconds and then rinsed withsaline. The above procedure is repeated for a given times, e.g., from 1to 30 times, (i.e., number of repetitions of digital rubbing tests whichimitate cleaning and soaking cycles).

Coating Intactness Tests

The intactness of a coating on the surface of a contact lens can betested according to Sudan Black stain test as follow. Contact lenseswith a coating (an LbL coating, a plasma coating, or any other coatings)are dipped into a Sudan Black dye solution (Sudan Black in the mixture˜80% mineral oil and ˜20% vitamin E oil). Sudan Black dye is hydrophobicand has a great tendency to be adsorbed by a hydrophobic material oronto a hydrophobic lens surface or hydrophobic spots on a partiallycoated surface of a hydrophobic lens (e.g., silicone hydrogel contactlens). If the coating on a hydrophobic lens is intact, no staining spotsshould be observed on or in the lens. All of the lenses under test arefully hydrated. Visible fine lines on lens surface may indicate thepresence of cracking of the crosslinked coatings.

Lens Surface Cracking Test

Excessive crosslinking of a coating layer can lead to surface cracksvisible under a darkfield microscope after rubbing a lens. The lenssurface cracking test is used to differentiate the severity of surfacecracking resulting from exposure of a lens to conditions and forces thatcould be encountered during routine and intended use of lenses.

Invert the lens confirmation by holding the edge of the lens between thethumb and index finger of one hand. The concave side of the lens shouldface the experimenter's body. With the thumb and/or index finger of theother hand, gently bend the top of the lens over the index fingerholding the lens until the lens confirmation inverts. Look for surfacecracks at 5× to 10× magnification under the darkfield stereomicroscope.If individual crack lines are clearly distinguishable, then the lensesare considered “yes” for cracking. If the lens appears to have long,cloudy, linear formations, but crack lines are not distinguishable, thenthese area maybe inspected at higher magnification as needed. If nocrack lines or long, cloudy, linear formations are visible, then thelens are considered “no” cracking. Lenses exhibiting no cracking 0 areconsidered better and are expected to exhibit smooth and soft surface.

Lens Surface Bead Test

The lens surface bead test is used to evaluate surface charges ofcontact lenses. The data generated from this method are the numbers ofbeads that are absorbed onto lens surface, and serve as an informationaltool indicating the surface charge property.

The beads of Dovex 1×4 chloride form 50-100 mesh (Lot #54898PJV SigmaAldrich CAS69011-19-4) are suspended in PBS. The lens is soaked inbead/PBS in a centrifuge tube. After on shaker at 300 rpm for 2 min, thelens is rinsed using PBS. The beads absorbed on lens surface are thenobserved under the dark field microscope. Image Pro software is used toanalyze the total count number of cationic beads. The total for cationicbeads is the total count number of the bead test.

Example 2

Synthesis of Glycerol Ether Containing PDMS Macromer (Macromer A)

Macromer A is prepared according to the procedures shown in Scheme 1

Synthesis of the Precursor

275.9 g of octamethylcyclotetrasiloxane (M.W. 296.62), 12.0 g of1,3,5,7-tetramethylcyclotetrasiloxane (M.W. 240.51), 9.7 g of1,3-bis(3-methacryloxypropyl) tetramethyldisiloxane (M.W. 386.63), and0.9 g of trifluoromethanesulfonic acid (M.W. 150.08) are weighed into a500 mL round bottom flask. After the reaction is run at 35° C. for 24 h,170 mL of 0.5% sodium hydrogen carbonate is added. The collected organicportion is further extracted five times with de-ionized water (170 mLper cycle). Anhydrous MgSO₄ is added to the collected organic solution,followed by ˜350 mL of additional CHCl₃, and the solution is thenstirred overnight. After filtration, the solvent is removed via Rotovap,followed by high vacuum. 102 g of final product (the precursor) isobtained.

Hydrosilylation Reaction with 3-Allyloxy-1,2-Propanediol to FormMacromer A

A small reactor is connected to a heater and air condenser with dryingtube. 21 g of toluene, 15 g of above precursor, and 5.03 g of3-allyloxy-1,2-propanediol are added to the reactor. After the solutiontemperature is stabilized at 30° C., 152 μL of Karstedt's catalyst (2 Pt% in xylene) is added. After 2 h, the conversion of Si—H of 100% basedon IR is achieved. The solution is then transferred to a flask,concentrated using Rotovop, followed by precipitation inactenotrile/water mixture (75/25) three times. After removal of solventvia Rotovop, followed by high vacuum, 12 g of hazy liquid is obtained.

Example 3

Synthesis of Glycerol Ether Containing PDMS Macromer (Macromer B)

Macromer B is prepared according to the procedures similar to whatdescribed in Example 2, except that the amount oftetramethylcyclotetrasiloxane in the first step for preparing precursoris approximately doubled. The obtained Macromer B has a structureformula

Example 4

Compatibility of Macromers with Hydrophilic Vinylic Monomers

Macromer A, prepared in Example 2, are used in preparing various lensformulations including from about 38% to about 58% by weight of at leastone hydrophilic vinylic monomer (DMA and/or NVP), to assess theircompatibility with relatively-high amount of hydrophilic vinylicmonomers. As control experiments,α,ω-dimethacryloxyethoxypropyl-terminated polydimethylsiloxane (M.W.4,500 g/mol) is used also as a macromer to prepare lens formulations inthe compatibility studies. Tables 1 and 2 show the compositions of thelens formulations. All lens formulations prepared from hydrophilizedpolydisiloxane crosslinker (macromer), Macromer A, are homogeneous(clear), whereas all the lens formulations prepared from unhydrophilizedpolydisiloxane crosslinker (macromer),α,ω-dimethacryloxyethoxypropyl-terminated polydimethylsiloxane, areinhomogeneous (cloudy).

TABLE 1 Composition (parts) Formulation No. 1 2 3 4 5 6 7 Macromer 25 3530 30 28 25 25 N—CH₃ BisAm 31 26 26 31 29 36 26 DMA 43 38 43 38 41 38 48

TABLE 2 Composition (parts) Formulation No. 8 9 10 11 Macromer 18 6 6 10MCR-M07 10.5 22.5 10.5 14.50 SIGMA 9 9 21 13 MMA 10 10 10 10 DMA 2 2 2 2NVP 49.4 49.4 49.4 49.4

Macromer A, Macromer B and control macromer(α,ω-dimethacryloxyethoxypropyl-terminated polydimethylsiloxane) areused to prepare three formulations with the following compositions:Macromer A or Macromer B or control macromer (10 parts); MCS-M11 (20parts); NVP (58 parts); MMA (10 parts); TEGDVE (0.1 part); TEGDMA (0.5part); Vazo 64 (0.8 part); and Norbloc (0.9 part).

It is found that the formulation including control macromer isinhomogeneous (cloudy) both at room temperature and at refrigeratetemperature (2-4° C.); the formulation including Macromer A ishomogeneous (clear) at room temperature but inhomogeneous (cloudy) atrefrigerate temperature (2-4° C.); the formulation including Macromer Bis homogeneous both at room temperature and at refrigerate temperature(2-4° C.). These results indicate that the higher content of hydrophilicsubstituents (glycerol ether pendant chains) in a macromer can improvethe capability of the macromer with hydrophilic vinylic monomers.

Example 5

Two lens formulations are prepared to have the following composition:Macromer A or B prepared in Example 2 (31.80%); N—CH₃ Bis Am (20.71%);DMA (23.24%); DC 1173 (1.01%); and 1-PrOH (23.21%). A prepared lensformulation is introduced into polypropylene lens molds and cured by UVirradiation to form contact lenses. Lenses are tested for propertiesaccording to the procedures described in Example 1. The properties(elastic modulus, E′; corrected oxygen permeability, Dkc; ionpermeability, IP, related to alsacon; water content) of resultant lensesare reported in Table 3.

TABLE 3 Lenses from Lenses from Lens properties Macromer A Macromer BModulus, E′ (MPa) 0.43 0.27 Dkc (barrers) 184 170 IP 3.5 2.5 WC % 29 29

Table 3 shows that when the molar ratio y/x, of the hydrophilizedsiloxane units over dimethylsiloxane units in the usedpolydiorganosiloxane vinylic crosslinker increases from about 0.054(Macromer A) to about 0.094 (Macromer B), the oxygen permeability ofresultant lenses decreases from about 184 Barrers to about 170 Barrers.

Lenses, made from both Macromer A and B, are tested for thermalstability as characterized by autoclave-induced change in lensproperties (E′, WC %, and D_(lens)). Table 4 shows that no significantautoclave-induced change in lens properties is observed for all thelenses made from Macromer A or B even after being subjected to 1, 7, 13,and 19-cycles of autoclave treatments respectively, i.e., having a goodthermal stability.

TABLE 4 Lenses from Macromer A Lenses from Macromer B E′ (MPa) WC %D_(lens) (mm) E′ (MPa) WC % D_(lens) (mm) AC (x1) 0.43 ± 0.04 29.1 ± 0.414.49 ± 0.07 0.27 ± 0.02 28.8 ± 0.4 14.33 ± 0.09 AC (x7) NA NA NA 0.24 ±0.01 29.2 ± 0.4 14.32 ± 0.16 AC (x13) 0.40 ± 0.01 29.8 ± 0.4 14.48 ±0.05 0.23 ± 0.02 29.3 ± 0.5 14.35 ± 0.28 AC (x19) 0.41 ± 0.01 29.8 ± 0.314.61 ± 0.05 0.25 29.5 ± 0.7 14.28 ± 0.12

Example 6

Synthesis of the Precursor

1935.04 g of Octamethylcyclotetrasiloxane (D4), 158.74 g of1,3,5,7-tetramethylcyclotetrasiloxane (D4H) and 106.33 g of1,3-BIS(3-methacryloxypropyl)tetramethyldisiloxane are weighted andpremixed in a flask and then charged to a 4-L jacked reactor equippedwith a mechanical motor, thermo couple and N₂ flow. After 4.4 g oftriflic Acid is spiked to the reaction flask. The reaction is thenperformed at 25° C. for about 14 hours. After the reaction is completed,the solution is diluted with 1000 mL of toluene and then neutralized bya solid base follow with one hour of stir. The final mixture is filteredwith 0.45 micron Glass Microfiber Filter and then concentrated onrotavap and then under low vacuum to remove the residual solvent in thepresence of 400-500 ppm of inhibitor. The resultant precursor is notpurified and determined to have a number average molecular weight ofabout 8K g/mol., an averaged x of about 92.6 (by NMR), and an averaged yof about 9.2 (by NMR).

Synthesis of the Glycerol Ether Containing PDMS Macromer

A 4 L jacket reactor is warmed up to 75° C. and purged with nitrogen for0.5 h. 3-allyloxy-1,2-propanediol (ca. 780.4 g, i.e., in a molar ratioof 5:1 over hydrosiloxane unit) the precursor prepared above (ca. 999.5g), potassium acetate (ca. 2.5 g) and isopropanol (ca. 1.2 L) are addedtherein. The mixture is stirred for about 20 minutes. About 1.6 mL (ca.30 ppm related to the precursor) of Karstedt's catalyst solution isinjected therein. The reaction mixture is stirred at 75° C. for aboutone hour. The reaction mixture is then cooled down to room temperatureand transferred to a separatory funnel for carrying out extractions toremove extra 3-allyloxy-1,2-propanediol starting materials. The crudeproduct after reaction is then extracted as following: first with 1.5 Lof a mixture of acetonitrile/water (9/1 v/v) for 42 hours and then with1000 g of a mixture of tetrahydrofuran (THF)/MeCN/water (450/350/200w/w/w) for 24 hours for three times. The weight of the product afterextraction is about 907.2 g.

After extraction, the silicone phase is stabilized with 100 mg (˜200ppm) of phenothiazine (PTZ) inhibitor in 10 mL of toluene. The solventis removed on rotary evaporator at 35° C. The weight of product at thistime is about 537.0 g. The product is diluted with 1000 g of toluene andfiltered with glass fiber filter covered by celite. After concentrationon rotary evaporator at 35° C., the weight of product is about 473.6 g.The product is diluted again with 1000 g of toluene, and then filteredwith 0.45 μm membrane. After concentration on rotary evaporator at 35°C., the weight of product is about 476.5 g. 100 mg (˜200 ppm) of2,6-di-tert-butyl-4-methylphenol (BHT) and 100 mg (˜200 ppm) of4-methoxyphenol (MEHQ) in 1.0 mL of toluene are added to stabilize theproduct. The product is dried under high vacuum at r.t. for 3 h.(Weight=458.62 g), and then at 60° C. for 3 h. The weight of finalmacromer is about 432.6 g. Yield: 74.7% based on half of siliconeprecursor. The solid content of macromers is determined by weight lossunder high vacuum at 50. Solid content: 96.1%. x=109.0, y=9.9 (by NMR).

Example 7

Synthesis of the Precursor

D4 (1067.04 g), D4H (86.64 g) and1,3-BIS(3-methacryloxypropyl)tetramethyldisiloxane (46.54 g) areweighted and premixed in a flask and then charged to a 4-L jackedreactor equipped with a mechanical motor, thermo couple and N₂ flow.After triflic Acid (2.4 g) is spiked to the reaction flask. The reactionis then performed at 25° C. for 14 hours. After the reaction iscompleted, the solution is diluted with 1000 mL of toluene and thenneutralized by a solid base follow with one hour of stir. The finalmixture is filtered with 0.45 micron Glass Microfiber Filter and thenconcentrated on rotavap and then under low vacuum to remove the residualsolvent in the presence of 400-500 ppm of inhibitor. The resultantprecursor is not purified and determined to have a number averagemolecular weight of about 8K g/mol., an averaged x of about 99.6 (byNMR), and an averaged y of about 9.4 (by NMR).

Synthesis of the Glycerol Ether Containing PDMS Macromer

A 4 L jacket reactor is warmed up to 75° C. and purged with nitrogen for0.5 h. 3-allyloxy-1,2-propanediol (ca. 837.9 g, i.e., in a molar ratioof 5:1 over hydrosiloxane unit), the precursor prepared above (ca.1075.1 g), potassium acetate (ca. 1.8 g) and isopropanol (ca. 0.9 L) areadded therein. The mixture is stirred for about 20 minutes. About 1.6 mL(ca. 30 ppm related to the precursor) of Karstedt's catalyst solution isinjected therein. The reaction mixture is stirred at 75° C. for aboutone hour. The reaction mixture is then cooled down to room temperatureand transferred to a separatory funnel for carrying out extractions toremove extra 3-allyloxy-1,2-propanediol starting materials. The crudeproduct after reaction is then extracted as following: first with 3.0 Lof a mixture of acetonitrile/water (9/1 v/v) for 24 hours, with 2.0 L ofa mixture of THF/MeCN/water (450/350/200 w/w/w) for 24 hours for twotimes, and finally with 2.0 L of a mixture of THF/MeCN/water(450/350/200 w/w/w) for 66 hours. The weight of the product afterextraction is about 1225.41 g.

The crude product is diluted with 2450 g of toluene and stabilized by245.1 mg of BHT and 245.3 mg of MEHQ inhibitors. The solution isfiltered with glass fiber filter covered by celite. After removalsolvent on rotary evaporator, the weight of product is about 1086.4 g.The product is diluted with 2000 g of toluene, and then filtered againthrough 0.45 μm membrane. After removal solvent on rotary evaporator at35° C., the weight is about 1089.2 g. The product is dried under highvacuum at room temperature for 20 h (Weight=1064.08 g), and then at 80°C. for 3 h. The final weight of the macromer is about 1049.9 g(theoretical: 846.12 g). Yield: 84.3%. The solid content of macromers isdetermined by weight loss under high vacuum at 50° C. for 24 h. Solidcontent: 98.0%. x=122.5, y=11.0 (by NMR).

Example 8

A lens formulation is prepared to have the following composition:Macromer A prepared in Example 2 (10 parts); MCR-M07 (30 parts); MMA (10parts); VMA (50 parts); TEGDMA (0.2 parts); and Vazo 64 (0.5 parts). Theprepared lens formulation is homogeneous (clear) both at roomtemperature and at refrigerate temperature (2-4° C.), indicatingMacromer A is compatible with VMA at least up to about 50% by weight.

Lenses which are cast-molded (thermally) in polypropylene molds have thefollowing properties: elastic modulus (0.52±0.01 MPa); elongation atbreak (245±128%); tensile strength (0.88±0.52 MPa); oxygen permeability(DKc=124.5±11 barrers).

Example 9

IPC Saline

IPC saline is prepared by mixing about 0.07% by weight ofPoly(AAm-co-AA) [poly(acrylamide-co-acrylic acid)] with about 0.35% byweight of PAE (polyamidoamine-ephichlorohydrin) in phosphate bufferedsaline and pre-treated at certain temperature for a desired time.Poly(AAm-co-AA)(90/10) partial sodium salt, poly(AAm-co-AA) 90/10, Mw200,000) is purchased from Polysciences, Inc. and used as received.After the heat pre-treatment, the IPC saline is filtered using a 0.22micron membrane filter and cooled down back to room temperature. 5 ppmhydrogen peroxide maybe added to the final IPC saline to preventbioburden growth and the IPC saline is filtered using a 0.22 micronmembrane filter.

Preparation of SiHy Lenses

A lens formulation is prepared by adding Macromer A prepared in Example2 (6 parts), AMA (0.1 part), TEGDMA (0.2 part), MMA (10 parts), EGMA (10parts), NVP (40 parts), MCR-M07 (34 parts), Norbloc (0.9 part), RB246(0.01 part) and VAZO 64 (0.5 part) into a clean bottle, with a stir barto mix at 600 rpm for 30 min at room temperature. After all the solid isdissolved, a filtration of the formulation is carried out by using 2.7um GMF filter.

The lens formulation prepared above is purged with nitrogen at roomtemperature for 30 to 35 minutes. The N₂-purged lens formulation isintroduced into polypropylene molds and thermally cured under thefollowing curing conditions: ramp from room temperature to 55° C. at aramp rate of about 7° C./minute; holding at 55° C. for about 30 minutes;ramp from 55° C. to 80° C. at a ramp rate of about 7° C./minute; holdingat 55° C. for about 30 minutes; ramp from 80° C. to 100° C. at a ramprate of about 7° C./minute; and holding at 100° C. for about 30 minutes.The molds are opened and the molded lenses are removed from the molds.

After demolding, silicone hydrogel contact lenses are subjected to a3-step coating process to form PAA coatings (i.e., base coatings) on thesilicone hydrogel contact lenses as follows. Silicone hydrogel contactlenses are first immersed in phosphate buffered saline (PBS, ca. 0.044w/w % NaH₂PO₄.H₂O, ca. 0.388 w/w/% Na₂HPO₄.2H₂O, and ca. 0.79 w/w %NaCl) for about 60 minutes at room temperature, second immersed in thePAA solution (ca. 0.5% by weight of polyacrylic acid (Mw 250000), pH2.0) for about 60 minutes at room temperature, and third rinsed with PBSfor about 5 minutes at room temperature.

SiHy lenses having a PAA base coating thereon prepared above are placedin polypropylene lens packaging shells (or blisters) (one lens pershell) with 0.6 mL of the IPC saline (half of the saline is added priorto inserting the lens). The blisters are then sealed with foil andautoclaved for about 45 minutes at about 121° C., forming SiHy contactlenses with crosslinked coatings (PAA-x-hydrophilic polymeric material)thereon.

The resultant SiHy lenses have an oxygen permeability (measuredaccording to polarographic method) of about 83 barrers, a bulk elasticmodulus of about 0.67 MPa, a water content of about 50% by weight, arelative ion permeability of about 11.0 relative to Alsacon lens, and awater contact angle of 29 degrees, a WBUT of 14 seconds. Some crackinglines are visible after rubbing the test lens and stained with SudanBlack. However, the lenses are very lubricious in a finger rubbing testand having a friction rating of about 0.5. When the lenses are testedfor lens surface charge according to the Positively Charged ParticlesAdhesion test, there are less than 71 positively-charged particles(DOWEX™ monosphere ion exchange resins) which are adhered onto lenseswith the crosslinked coating.

What is claimed is:
 1. A silicone hydrogel contact lens comprising acrosslinked polymeric material which comprises units of apolydiorganosiloxane vinylic crosslinker of formula (1)

in which: υ1 is an integer of from 30 to 500 and ω1 is an integer offrom 1 to 75, provided that ω1/υ1 is from about 0.035 to about 0.15; X₀is O or NR′ in which R′ is hydrogen or C₁-C₁₀-alkyl; R₁ is hydrogen ormethyl; R₂ and R₃ independently of each other are a substituted orunsubstituted C₁-C₁₀ alkylene divalent radical or a divalent radical of—R₅—O—R₆— in which R₅ and R₆ independently of each other are asubstituted or unsubstituted C₁-C₁₀ alkylene divalent radical; R₄ is amonovalent radical of formula (6)

q1 is zero or 1; n1 is an integer of 2 to 4; and R₇ is hydrogen ormethyl, wherein the polydiorganosiloxane vinylic crosslinker has anumber average molecular weight of from about 3000 Daltons to about80,000 Daltons.
 2. The silicone hydrogel contact lens of claim 1,wherein in formula (1) X₀ is O.
 3. The silicone hydrogel contact lens ofclaim 2, wherein in formula (1) ω1/υ1 is from about 0.040 to about 0.12.4. The silicone hydrogel contact lens of claim 3, wherein in formula (6)n1 is 3 and q1 is
 1. 5. The silicone hydrogel contact lens of claim 4,wherein the crosslinked polymeric material comprises units of at leastone hydrophilic vinylic monomer.
 6. The silicone hydrogel contact lensof claim 5, wherein said at least one hydrophilic vinylic monomer isselected from the group consisting of N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide, (meth)acrylamide, N-hydroxyethyl (meth)acrylamide,N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerolmethacrylate, polyethylene glycol (meth)acrylate having a number averagemolecular weight of up to 1500, polyethylene glycol C₁-C₄-alkyl ether(meth)acrylate having a number average molecular weight of up to 1500,N-[tris(hydroxymethyl)methyl]-acrylamide, N-vinyl formamide, N-vinylacetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide,N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone,5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone,(meth)acrylic acid, ethylacrylic acid, and combinations thereof.
 7. Thesilicone hydrogel contact lens of claim 5, wherein said at least onehydrophilic vinylic monomer is N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or combinations thereof.
 8. The silicone hydrogel contactlens of claim 4, wherein the crosslinked polymeric material comprisesunits of a siloxane-containing vinylic monomer.
 9. The silicone hydrogelcontact lens of claim 8, wherein the siloxane-containing vinylic monomeris 3-acrylamidopropyl-bis(trimethylsiloxy)-methylsilane, 3-N-methylacrylamidopropylbis(trimethylsiloxy)methylsilane,N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide,N-[tris(dimethylpropylsiloxy)-silylpropyl]-(meth)acrylamide,N-[tris(dimethylphenylsiloxy)silylpropyl] (meth)acrylamide,N-[tris(dimethylethylsiloxy)-silylpropyl] (meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)propyl)-2-methyl acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)propyl)acrylamide,N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)propyl]-2-methylacrylamide,N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide,N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide,N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methylacrylamide,N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide,N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide,N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide,N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide,N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide,3-methacryloxy propylpentamethyldisiloxane,tris(trimethylsilyloxy)silylpropyl methacrylate,(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane),(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane,3-methacryloxyethoxypropyloxy-propyl-bis(trimethylsiloxy)methylsilane,N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propylvinyl carbonate,3-(vinyloxycarbonylthio)propyl-tris(trimethyl-siloxy)silane,3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate,3-[tris(trimethylsiloxy)silyl] propyl allyl carbamate,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate,t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinylcarbonate, trimethylsilylmethyl vinyl carbonate, or combinationsthereof.
 10. The silicone hydrogel contact lens of claim 8, wherein thesiloxane-containing vinylic monomer is a polycarbosiloxane vinylicmonomer.
 11. The silicone hydrogel contact lens of claim 8, wherein thesiloxane-containing vinylic monomer is a polydimethylsiloxane-containingvinylic monomer.
 12. The silicone hydrogel contact lens of claim 11,wherein the polydimethylsiloxane-containing vinylic monomer is3-(meth)acryloxy-2-hydroxypropyloxy)propyl-bis(trimethylsiloxy)methylsilane,3-(meth)acryloxyethoxy-propyloxypropyl-bis(trimethylsiloxy)methylsilane,3-(meth)acrylamidopropyl-bis(trimethylsiloxy)-methylsilane, 3-N-methyl(meth)acrylamidopropylbis(trimethylsiloxy) methylsilane, amono-(meth)acryloxy-terminated polydimethylsiloxane, or amono-(meth)acrylamido-terminated polydimethylsiloxane.
 13. The siliconehydrogel contact lens of claim 11, wherein thepolydimethylsiloxane-containing vinylic monomer ismono-3-methacryloxypropyl terminated, mono-butyl terminatedpolydimethylsiloxane or mono-(3-methacryloxy-2-hydroxypropyloxy)propylterminated, mono-butyl terminated polydimethylsiloxane.
 14. The siliconehydrogel contact lens of claim 8, wherein the crosslinked polymericmaterial comprises units of a hydrophobic vinylic monomer free ofsilicone.
 15. The silicone hydrogel contact lens of claim 14, whereinthe hydrophobic vinylic monomer free of silicone is methylacrylate,ethyl-acrylate, propylacrylate, isopropylacrylate, cyclohexylacrylate,2-ethylhexylacrylate, methylmethacrylate, ethylmethacrylate,propylmethacrylate, vinyl acetate, vinyl propionate, vinyl butyrate,vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidenechloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinyl ethyl ether,perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornylmethacrylate, trifluoroethyl methacrylate, hexafluoro-isopropylmethacrylate, or hexafluorobutyl methacrylate.
 16. The silicone hydrogelcontact lens of claim 14, wherein the crosslinked polymeric materialcomprises units of a non-silicone vinylic crosslinker.
 17. The siliconehydrogel contact lens of claim 14, wherein the non-silicone vinyliccrosslinker is selected from the group consisting of ethyleneglycoldi-(meth)acrylate, diethyleneglycol di-(meth)acrylate, triethyleneglycoldi-(meth)acrylate, tetraethyleneglycol di-(meth)acrylate, glyceroldi-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanedioldi-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol1,3-diglycerolate di-(meth)acrylate,ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate,bis[2-(meth)acryloxyethyl] phosphate, tri methylolpropanedi-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuan,diacrylamide, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine,N,N-di(meth)acryloyl-N-ethylamine, N,N′-methylene bis(meth)acrylamide,N,N′-ethylene bis(meth)acrylamide, N,N′-dihydroxyethylenebis(meth)acrylamide, N,N′-propylene bis(meth)acrylamide,N,N′-2-hydroxypropylene bis(meth)acrylamide, N,N′-2,3-dihydroxybutylenebis(meth)acrylamide, 1,3-bis(meth)acrylamidepropane-2-yl dihydrogenphosphate, piperazine diacrylamide, vinyl methacrylate,allylmethacrylate, allylacrylate, N-allyl-methacrylamide,N-allyl-acrylamide, tetraethyleneglycol divinyl ether, triethyleneglycoldivinyl ether, diethyleneglycol divinyl ether, ethyleneglycol divinylether, triallyl isocyanurate, triallyl cyanurate, trimethylopropanetrimethacrylate, pentaerythritol tetramethacrylate, bisphenol Adimethacrylate, or a reaction product of a diamine with anepoxy-containing vinylic monomer, and combinations, wherein the diamineis selected from the group consisting ofN,N′-bis(hydroxyethyl)ethylenediamine, N,N′-dimethylethylenediamine,ethylenediamine, N,N′-dimethyl-1,3-propanediamine,N,N′-diethyl-1,3-propanediamine, propane-1,3-diamine,butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine,isophorone diamine, and combinations thereof, and wherein theepoxy-containing vinylic monomer is selected from the group consistingof glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether,and combinations thereof.
 18. The silicone hydrogel contact lens ofclaim 16, wherein the crosslinked polymeric material comprises units ofa UV-absorbing vinylic monomer.
 19. The silicone hydrogel contact lensof claim 18, wherein the UV-absorbing vinylic monomer is selected fromthe group consisting of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole,2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl) benzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacrylamidophenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloxypropyl-3′-t-butyl-phenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methacryloxypropylphenyl) benzotriazole,2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate,2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate,3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate,3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate,3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzylmethacrylate,2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate,2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzylmethacrylate,4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol,2-{2′-Hydroxy-3′-tert-5-[3″-(4″-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole,phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-,2-(2′-hydroxy-5′-methacryloxy-ethylphenyl) benzotriazole (2-Propenoicacid, 2-methyl-, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethylester,2-{2′-Hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropoxy]-phenyl}-5-methoxy-2H-benzotriazole,2-[2′-Hydroxy-3′-tert-butyl-5′-(3′-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole,2-(2′-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole,2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(2-Hydroxy-3-methallyl-5-methylphenyl)-2H-benzotriazole,2-3′-t-butyl-2′-hydroxy-5′-(3″-dimethylvinylsilylpropoxy)-2′-hydroxy-phenyl)-5-methoxybenzotriazole,2-(2′-hydroxy-5′-methacryloylpropyl-3′-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole,2-(2′-hydroxy-5′-acryloylpropyl-3′-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole,2-Methylacrylic acid3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propylester,2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethylmethacrylate; Phenol,2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl);2-[2-Hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole;Phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer, andcombinations thereof.